Isoxazoline derivatives and herbicides containing the same as the active ingredient

ABSTRACT

The isoxazoline derivative of the present invention is represented by the following general formula [I]: 
                 
 
[wherein Q is a group represented by —S(O) n —(CR 5 R 6 ) m - (wherein n is an integer of 0 to 2, m is an integer of 1 to 3, and R 5  and R 6  are a hydrogen atom, a cyano group, an alkoxycarbonyl group, if an alkyl group or the like); R 1  and R 2  are a hydrogen atom, all optionally substituted alkyl group, an alkoxycarbonyl group, an optionally substituted phenyl group or the like; R 3  and R 4  are a hydrogen atom, an optionally substituted alkyl group, a cycloalkyl group or the like; Y is a hydrogen atom, an alkoxycarbonyl group, a carboxyl group, an alkenyl group, an optionally substituted alkyl group or an optionally substituted phenyl group]. The herbicide of the present invention contains the above isoxazoline derivative as the active ingredient.

This application is a 371 of PCT/JP00/05325 filed Aug. 9, 2000.

TECHNICAL FIELD

The present invention relates to a novel isoxazoline derivative and a herbicide containing it as the active ingredient.

BACKGROUND ART

The herbicidal activities of isoxazoline derivatives are reported in, for example, JP-A-8-225548, JP-A-9-328477 and JP-A-9-328483. The compounds described in these literatures have a chloromethyl group mainly at the 5-position of the isoxazoline ring, and the isoxazoline derivative of the present invention has been unknown.

Herbicides used for useful crops are desired to be applied to soil or foliage, show a sufficient herbicidal effect at a low amount, and exhibit high selectivity between crop and weeds. The compounds described in the above literatures are not fully satisfactory in these respects.

DISCLOSURE OF THE INVENTION

In view of the above situation, the present inventors made a study on herbicidal effect and selectivity between crop and weeds. As a result, the present inventors found out that a novel isoxazoline derivative is superior in herbicidal effect and selectivity between crop and weeds. The present invention has been completed based on the finding.

The present invention provides:

-   -   (1) an isoxazoline derivative represented by the following         general formula [I] or a salt thereof:         (wherein Q is a group represented by —S(O), —(CR₅R₆)_(m)-         (wherein n is an integer of 0 to 2, m is an integer of 1 to 3,         and R₅ and R₆ are each independently a hydrogen atom, a cyano         group, an alkoxycarbonyl group or a C₁ to C₆ alkyl group);

-   R1 and R₂ are a hydrogen atom, a C₁ to C₈ alkyl group, [which may be     substituted with C₃ to C₈ cycloalkyl group, C₁ to C₆ alkoxy group,     C₁ to C₆ alkylcarbonyl group, C₁ to C₆ alkylthio group, C₁ to C₆     alkylsulfinyl group, C₁ to C₆ alkylsulfonyl group, C₁ to C₆     alkylamino group, di(C₁ to C₆ alkyl)amino group, hydroxyl group,     cyano group, C₁ to C₆ alkoxycarbonyl group, C₁ to C₆     alkylamino-carbonyl group, di(C₁ to C₆ alkyl)aminocarbonyl group,     (C₁ to C₆ alkylthio)carbonyl group, carboxyl group, optionally     substituted benzyloxy group, optionally substituted phenoxy group,     or optionally substituted phenyl group], a C₃ to C₈ cycloalkyl     group, a C₁ to C₆ alkoxycarbonyl group, a C₁ to C₆     alkylaminocarbonyl group, a di(C₁ to C₆ alkyl)aminocarbonyl group,     or a (C₁ to C₆ alkylthiocarbonyl group, carboxyl group or optionally     substituted) phenyl group, or, R₁ and R₂ may form a C₃ to C₇ spiro     ring together with the carbon atom to which they bond;

-   R₃ and R₄ are a hydrogen atom, a C₁ to C₈ alkyl group (which may be     substituted with 1 to 3 same or different halogen atoms, C₃ to C₈     cycloalkyl groups or C₁ to C₆ alkoxy groups) or a C₃ to C₈     cycloalkyl group, and R₃ and R₄ may form a C₃ to C₇ spiro ring     together with the carbon atom to which they bond, or, R₁, R₂, R₃ and     R₄ may form a 5- to 8-membered ring together with the carbon atoms     to which they bond;

-   Y is a hydrogen atom, a C₁ to C₆ alkoxycarbonyl group, a carboxyl     group, a C₂ to C₆ alkenyl group, a C₁ to C₁₀ alkyl group [which may     be substituted with 1 to 3 same or different halogen atoms, C₁ to C₆     alkoxy groups, C₂ to C₆ alkenyloxy groups, C₂ to C₆ alkynyloxy     groups, optionally substituted benzyloxy gorups, C₁ to C₆     alkoxycarbonyl groups, carboxyl groups, hydroxyl groups or formyl     groups], or a phenyl group substituted with 1 to 5 same or different     R₇s;

-   each R₇ is a hydrogen atom, a C₁ to C₆ alkyl group [which may be     substituted with 1 to 3 same or different halogen atoms, C₁ to C₆     alkoxy groups, hydroxyl groups, C₁ to C₆ alkylthio groups, C₁ to C₆     alkylsulfinyl groups, C₁ to C₆ alkylsulfonyl groups, C₁ to C₆     alkylamino groups, di(C₁ to C₆)alkylamino groups, cyano groups or     optionally substituted phenoxy groups], a C₁ to C₆ alkoxy group     (which may be substituted with 1 to 3 same or different halogen     atoms, C₁ to C₆ alkoxy groups, C₂ to C₆ alkenyl groups, C₂ to C₆     alkynyl groups, C₁ to C₆ alkoxycarbonyl groups, C₁ to C₆     alkylcarbonyl groups or C₃ to C₈ cycloalkyl groups), a C₂ to C₆     alkenyl group, a C₃ to C₈ cycloalkyloxy group, a C₁ to C₆ alkylthio     group (which may be substituted with 1 to 3 same or different     halogen atoms or C₁ to C₆ alkoxy groups), a C₁ to C₆ alkylsulfinyl     group (which may be substituted with 1 to 3 same or different     halogen atoms or C₁ to C₆ alkoxy groups), a C₁ to C₆ alkylsulfonyl     group (which may be substituted with 1 to 3 same or different     halogen atoms or C₁ to C₆ alkoxy groups), an optionally substituted     benzyloxy group, an amino group [which may be substituted with C₁ to     C₆ alkyl group, C₁ to C₆ alkylsulfonyl group, C₁ to C₆ alkylcarbonyl     (C₁ to C₆ alkyl) group or C₁ to C₆ alkylsulfonyl (C₁ to C₆ alkyl)     group], a di(C₁ to C₆ alkyl)amino group, a halogen atom, a cyano     group, a nitro group, a C₁ to C₆ alkoxycarbonyl group, a C₃ to C₈     cycloalkyloxycarbonyl group, a carboxyl group, a C₂ to C₆     alkenyloxycarbonyl group, a C₂ to C₆ alkynyloxycarbonyl group, an     optionally substituted benzyloxycarbonyl group, an optionally     substituted phenoxycarbonyl group or a C₁ to C₆ alkylcarbonyloxy     group).     -   (2) a herbicide containing, as the active ingredient, an         isoxazoline derivative or its salt set forth in the above (1).

BEST MODE FOR CARRYING OUT THE INVENTION

The definitions of the terms used in the present specification are given below.

“Halogen atom” refers to a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

“Alkyl group” refers to a C₁ to C₁₀ straight or branched chain alkyl group unless other wise specified; and there can be mentioned, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, 3,3-dimethylbutyl group, heptyl group and octyl group.

“Cycloalkyl group” refers to a C₃ to C₈ cycloalkyl group; and there can be mentioned, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group.

“Alkoxy group” refers to an (alkyl)-O- group wherein the alkyl moiety has the above definition; and there can be mentioned, for example, methoxy group and ethoxy group.

“Alkylthio group”, “alkylsulfinyl group” and “alkylsulfonyl group” refer, respectively, to an (alkyl)-S— group, an (alkyl)-SO— group and an (alkyl)-SO₂— group, in each of which the alkyl moiety has the above definition; and there can be mentioned, for example, methylthio group, ethylthio group, methylsulfinyl group, methylsulfonyl group and ethylsulfonyl group.

“Alkenyl group” refers to a C₂ to C₆ straight or branched chain alkenyl group; and there can be mentioned, for example, ethenyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group and 2-pentenyl group.

“Alkynyl group” refers to a C₂ to C₆ straight or branched chain alkynyl group; and there can be mentioned, for example, ethinyl group, 2-propynyl group, 2-butinyl group and 3-butinyl group.

“Alkenyloxy group” and “alkynyloxy group” refer, respectively, to an (alkenyl)-O— group and an (alkynyl)-O— group, in each of which the alkenyl or alkynyl moiety has the above definition; and there can be mentioned, for example, 2-propenyloxy group and 2-propynyloxy group.

“Alkylamino group” and “dialkylamino group” refer, respectively, to an (alkyl)-NH— group and an (alkyl)₂—N— group, in each of which the alkyl moiety has the above definition; and there can be mentioned, for example, methylamino group, ethylamino group and dimethylamino group.

“Alkylcarbonyl group”, “(alkylthio)carbonyl group”, “alkoxycarbonyl group”, “alkylaminocarbonyl group” and “dialkylaminocarbonyl group” refer, respectively, to an (alkyl)-CO— group, an (alkylthio)-CO— group, an (alkoxy)-CO— group, an (alkylamino)-CO— group and a (dialkylamino)-CO— group, in each of which the alkyl, alkylthio, alkoxy, alkylamino or dialkylamino moiety has the above definition; and there can be mentioned, for example, acetyl group, methylthiocarbonyl group, ethoxycarbonyl group, methoxycarbonyl group, methylaminocarbonyl group and dimethylaminocarbonyl group.

“Alkylaminocarbonylamino group”, “dialkylaminocarbonylamino group” and “alkoxycarbonylamino group” refer, respectively, to an (alkylaminocarbonyl)-NH— group, a (dialkylaminocarbonyl)-NH— group and an (alkxoycarbonyl)-NH— group, in each of which the alkylaminocarbonyl, dialkylaminocarbonyl or alkoxycarbonyl moiety has the above definition; and there can be mentioned, for example, methylaminocarbonylamino group, dimethylaminocarbonylamino group and methoxycarbonylamino group.

“Optionally substituted phenyl group” includes phenyl groups each having, on the phenyl ring, 1 to 5 substituents such as halogen atom(s), C₁ to C₆ alkyl group(s), C₁ to C₆ alkoxy group(s) and the like.

“Optionally substituted phenoxy group” includes phenoxy groups each having, on the phenyl ring, 1 to 5 substituents such as halogen atom (s), C₁ to C₆ alkyl group(s), C₁ to C₆ alkoxy group(s) and the like.

“Optionally substituted benzyloxy group” includes benzyloxy groups each having, on the phenyl ring and at the benzylic position, 1 to 7 substituents such as halogen atom(s), C₁ to C₆ alkyl group(s), C₁ to C₆ alkoxy group(s) and the like.

“Optionally substituted phenoxycarbonyl group” includes phenoxycarbonyl groups each having, on the phenyl ring, 1 to 5 substituents such as halogen atom(s), C₁ to C₆ alkyl group(s), C₁ to C₆ alkoxy group(s) and the like.

“Salt” refers to a salt between the carboxyl group, sulfonyl group, hydroxyl group, amino group or other group present in the compound of the general formula [1] and a metal, an organic base, an organic acid or an inorganic acid. As the metal, there can be mentioned alkali metals such as sodium, potassium and the like, and alkaline earth metals such as magnesium, calcium and the like. As the organic base, there can be mentioned triethylamine, diisopropylamine, etc. As the organic acid, there can be mentioned acetic acid, oxalic acid, maleic acid, p-toluenesulfonic acid, etc. As the inorganic acid, there can be mentioned hydrochloric acid, sulfuric acid, nitric acid, etc.

Preferable examples of the compound of the general formula [I] are those compounds wherein R₁ and R₂ are a C₁ to C₃ alkyl group or a C₁ to C₃ alkoxyalkyl group, R₃ and R₄ are a hydrogen atom or a C₁ to C₃ alkyl group, Q is a group represented by —S(O)_(n)-(CR₅R₆)_(m)-, R₅ and R₆ are a hydrogen atom or a C₁ to C₃ alkyl group, n is 2, m is 1, and Y is an optionally substituted phenyl group or a C₂ to C₁₀ alkyl group.

Next, representative examples of the present compound of the general formula [I] are shown in Tables 1 to 24. However, the present compound is not restricted to these. Incidentally, the No. of each compound is used also in the later description.

The following abbreviations used in the following tables indicate the following groups.

Me: methyl group Et: ethyl group Pr: n-propyl group Pr-i: isopropyl group Pr-c: cyclopropyl group Bu: n-butyl group Bu-i: isobutyl group Bu-s: sec-butyl group Bu-t: tert-butyl group Bu-c: cyclobutyl group Pen: n-pentyl group Hex: n-hexyl group Pen-c: cyclopentyl group Hex-c: cyclohexyl group Ph: phenyl group Bn: benzyl group

TABLE 1

Melting point (° C.) or Compound refractive index No. R₁ R₂ R₃ R₄ Q Y (n_(D) ²⁰) 1-1  Me Me H H SO₂CH₂ Ph 108.5-110   1-2  Me Me H H SO₂CH₂ Ph(2-Cl) 71-72 1-3  Me Me H H SO₂CH₂ Ph(3-Cl) 91.5-92   1-4  Me Me H H SO₂CH₂ Ph(4-Cl)   138-138.5 1-5  Me Me H H SO₂CH₂ Ph(2-Me) 96-97 1-6  Me Me H H SO₂CH₂ Ph(3-Me) 78-79 1-7  Me Me H H SO₂CH₂ Ph(4-Me) 97-98 1-8  Me Me H H SO₂CH₂ Ph(2-Et) 1.5390 1-9  Me Me H H SO₂CH₂ Ph(3-Et) 1-10 Me Me H H SO₂CH₂ Ph(4-Et) 1-11 Me Me H H SO₂CH₂ Ph(2-Pr) 1-12 Me Me H H SO₂CH₂ Ph(3-Pr) 1-13 Me Me H H SO₂CH₂ Ph(4-Pr) 1-14 Me Me H H SO₂CH₂ Ph(2-Pr-i) 1-15 Me Me H H SO₂CH₂ Ph(3-Pr-i) 1-16 Me Me H H SO₂CH₂ Ph(4-Pr-i) 1-17 Me Me H H SO₂CH₂ Ph(2-Bu) 1-18 Me Me H H SO₂CH₂ Ph(3-Bu) 1-19 Me Me H H SO₂CH₂ Ph(4-Bu) 1-20 Me Me H H SO₂CH₂ Ph(2-Bu-i)

TABLE 2 Melting Com- point (° C.) or pound refractive index No. R₁ R₂ R₃ R₄ Q Y (n_(D) ²⁰) 1-21 Me Me H H SO₂CH₂ Ph(3-Bu-i) 1-22 Me Me H H SO₂CH₂ Ph(4-Bu-i) 1-23 Me Me H H SO₂CH₂ Ph(2-Bu-s) 1-24 Me Me H H SO₂CH₂ Ph(3-Bu-s) 1-25 Me Me H H SO₂CH₂ Ph(4-Bu-s) 1-26 Me Me H H SO₂CH₂ Ph(2-Bu-t) 1-27 Me Me H H SO₂CH₂ Ph(3-Bu-t) 1-28 Me Me H H SO₂CH₂ Ph(4-Bu-t) 1-29 Me Me H H SO₂CH₂ Ph(2-Hex) 1-30 Me Me H H SO₂CH₂ Ph(3-Hex) 1-31 Me Me H H SO₂CH₂ Ph(4-Hex) 1-32 Me Me H H SO₂CH₂ Ph(2-F) 102-103 1-33 Me Me H H SO₂CH₂ Ph(3-F)   105-105.5 1-34 Me Me H H SO₂CH₂ Ph(4-F)   138-138.5 1-35 Me Me H H SO₂CH₂ Ph(2-Br) 77-78 1-36 Me Me H H SO₂CH₂ Ph(3-Br) 1-37 Me Me H H SO₂CH₂ Ph(4-Br) 1-38 Me Me H H SCH₂ Ph(2,6-F₂) 77-80 1-39 Me Me H H SO₂CH₂ Ph(2,6-F₂) 110-111 1-40 Me Me H H SO₂CH₂ Ph(2-OMe) 94-95 1-41 Me Me H H SO₂CH₂ Ph(3-OMe) 89-90 1-42 Me Me H H SO₂CH₂ Ph(4-OMe) 122-124 1-43 Me Me H H SO₂CH₂ Ph(2-OEt) 76-79 1-44 Me Me H H SO₂CH₂ Ph(3-OEt) 1-45 Me Me H H SO₂CH₂ Ph(4-OEt)

TABLE 3 Melting point (° C.) or Compound refractive index No. R₁ R₂ R₃ R₄ Q Y (n_(D) ²⁰) 1-46 Me Me H H SO₂CH₂ Ph(2-OPr) 67-68 1-47 Me Me H H SO₂CH₂ Ph(3-OPr) 1-48 Me Me H H SO₂CH₂ Ph(4-OPr) 1-49 Me Me H H SO₂CH₂ Ph(2-OPr-i) 73-74 1-50 Me Me H H SO₂CH₂ Ph(3-OPr-i) 1-51 Me Me H H SO₂CH₂ Ph(4-OPr-i) 1-52 Me Me H H SO₂CH₂ Ph(2-OHex) 1-53 Me Me H H SO₂CH₂ Ph(3-OHex) 1-54 Me Me H H SO₂CH₂ Ph(4-OHex) 1-55 Me Me H H SO₂CH₂ Ph(2-OCHF₂) 80-81 1-56 Me Me H H SO₂CH₂ Ph(3-OCHF₂) 51-53 1-57 Me Me H H SO₂CH₂ Ph(4-OCHF₂) 1-58 Me Me H H SO₂CH₂ Ph(2-OCF₃) 1.492 1-59 Me Me H H SO₂CH₂ Ph(3-OCF₃) 82-84 1-60 Me Me H H SO₂CH₂ Ph(4-OCF₃) 1-61 Me Me H H SO₂CH₂ Ph(2-OCH₂CH₂OMe) 1-62 Me Me H H SO₂CH₂ Ph(3-OCH₂CH₂OMe) 1-63 Me Me H H SO₂CH₂ Ph(4-OCH₂CH₂OMe) 1-64 Me Me H H SO₂CH₂ Ph(2-SMe) 1-65 Me Me H H SO₂CH₂ Ph(3-SMe) 1-66 Me Me H H SO₂CH₂ Ph(4-SMe) 1-67 Me Me H H SO₂CH₂ Ph(2-SEt) 1-68 Me Me H H SO₂CH₂ Ph(3-SEt) 1-69 Me Me H H SO₂CH₂ Ph(4-SEt) 1-70 Me Me H H SO₂CH₂ Ph(2-SPr)

TABLE 4 Melting point (° C.) or Compound refractive index No. R₁ R₂ R₃ R₄ Q Y (n_(D) ²⁰) 1-71 Me Me H H SO₂CH₂ Ph(3-SPr) 1-72 Me Me H H SO₂CH₂ Ph(4-SPr) 1-73 Me Me H H SO₂CH₂ Ph(2-SBu) 1-74 Me Me H H SO₂CH₂ Ph(3-SBu) 1-75 Me Me H H SO₂CH₂ Ph(4-SBu) 1-76 Me Me H H SO₂CH₂ Ph(2-SHex) 1-77 Me Me H H SO₂CH₂ Ph(3-SHex) 1-78 Me Me H H SO₂CH₂ Ph(4-SHex) 1-79 Me Me H H SO₂CH₂ Ph(2-SCHF₂) 1-80 Me Me H H SO₂CH₂ Ph(3-SCHF₂) 1-81 Me Me H H SO₂CH₂ Ph(4-SCHF₂) 1-82 Me Me H H SO₂CH₂ Ph(2-SCH₂CH₂OMe) 1-83 Me Me H H SO₂CH₂ Ph(3-SCH₂CH₂OMe) 1-84 Me Me H H SO₂CH₂ Ph(4-SCH₂CH₂OMe) 1-85 Me Me H H SO₂CH₂ Ph(2-SOMe) 1-86 Me Me H H SO₂CH₂ Ph(3-SOMe) 1-87 Me Me H H SO₂CH₂ Ph(4-SOMe) 1-88 Me Me H H SO₂CH₂ Ph(2-SOEt) 1-89 Me Me H H SO₂CH₂ Ph(3-SOEt) 1-90 Me Me H H SO₂CH₂ Ph(4-SOEt) 1-91 Me Me H H SO₂CH₂ Ph(2-SOPr) 1-92 Me Me H H SO₂CH₂ Ph(3-SOPr) 1-93 Me Me H H SO₂CH₂ Ph(4-SOPr) 1-94 Me Me H H SO₂CH₂ Ph(2-SOBu) 1-95 Me Me H H SO₂CH₂ Ph(3-SOBu)

TABLE 5 Melting point (° C.) or Compound refractive index No. R₁ R₂ R₃ R₄ Q Y (n_(D) ²⁰) 1-96 Me Me H H SO₂CH₂ Ph(4-SOBu) 1-97 Me Me H H SO₂CH₂ Ph(2-SOHex) 1-98 Me Me H H SO₂CH₂ Ph(3-SOHex) 1-99 Me Me H H SO₂CH₂ Ph(4-SOHex) 1-100 Me Me H H SO₂CH₂ Ph(2-SOCH₂CF₃) 1-101 Me Me H H SO₂CH₂ Ph(3-SOCH₂CF₃) 1-102 Me Me H H SO₂CH₂ Ph(4-SOCH₂CF₃) 1-103 Me Me H H SO₂CH₂ Ph(2-SOCH₂CH₂OMe) 1-104 Me Me H H SO₂CH₂ Ph(3-SOCH₂CH₂OMe) 1-105 Me Me H H SO₂CH₂ Ph(4-SOCH₂CH₂OMe) 1-106 Me Me H H SO₂CH₂ Ph(2-SO₂Me) 97-98 1-107 Me Me H H SO₂CH₂ Ph(3-SO₂Me) 1-108 Me Me H H SO₂CH₂ Ph(4-SO₂Me) 1-109 Me Me H H SO₂CH₂ Ph(2-SO₂Et) 1-110 Me Me H H SO₂CH₂ Ph(3-SO₂Et) 1-111 Me Me H H SO₂CH₂ Ph(4-SO₂Et) 1-112 Me Me H H SO₂CH₂ Ph(2-SO₂Pr) 1-113 Me Me H H SO₂CH₂ Ph(3-SO₂Pr) 1-114 Me Me H H SO₂CH₂ Ph(4-SO₂Pr) 1-115 Me Me H H SO₂CH₂ Ph(2-SO₂Bu) 1-116 Me Me H H SO₂CH₂ Ph(3-SO₂Bu) 1-117 Me Me H H SO₂CH₂ Ph(4-SO₂Bu) 1-118 Me Me H H SO₂CH₂ Ph(2-SO₂Hex) 1-119 Me Me H H SO₂CH₂ Ph(3-SO₂Hex) 1-120 Me Me H H SO₂CH₂ Ph(4-SO₂Hex)

TABLE 6 Melting point (° C.) or Compound refractive index No. R₁ R₂ R₃ R₄ Q Y (n_(D) ²⁰) 1-121 Me Me H H SO₂CH₂ Ph(2-SO₂CH₂CH₂OMe) 1-122 Me Me H H SO₂CH₂ Ph(3-SO₂CH₂CH₂OMe) 1-123 Me Me H H SO₂CH₂ Ph(4-SO₂CH₂CH₂OMe) 1-124 Me Me H H SO₂CH₂ Ph(2-SO₂CH₂CF₃) 1-125 Me Me H H SO₂CH₂ Ph(3-SO₂CH₂CF₃) 1-126 Me Me H H SO₂CH₂ Ph(4-SO₂CH₂CF₃) 1-127 Me Me H H SO₂CH₂ Ph(2-CH₂OPh) 1-128 Me Me H H SO₂CH₂ Ph(3-CH₂OPh) 1-129 Me Me H H SO₂CH₂ Ph(4-CH₂OPh) 1-130 Me Me H H SO₂CH₂ Ph(2-CH₂OPh(2-Cl)) 1-131 Me Me H H SO₂CH₂ Ph(3-CH₂OPh(3-Me)) 1-132 Me Me H H SO₂CH₂ Ph(4-CH₂OPh(4-OMe)) 1-133 Me Me H H SO₂CH₂ Ph(2-NHMe) 1-134 Me Me H H SO₂CH₂ Ph(3-NHMe) 1-135 Me Me H H SO₂CH₂ Ph(4-NHMe) 1-136 Me Me H H SO₂CH₂ Ph(2-N(Me)₂) 1-137 Me Me H H SO₂CH₂ Ph(3-N(Me)₂) 1-138 Me Me H H SO₂CH₂ Ph(4-N(Me)₂) 1-139 Me Me H H SO₂CH₂ Ph(2-CN) 120-122 1-140 Me Me H H SO₂CH₂ Ph(3-CN) 1-141 Me Me H H SO₂CH₂ Ph(4-CN) 1-142 Me Me H H SO₂CH₂ Ph(2-NO₂) 102-103 1-143 Me Me H H SO₂CH₂ Ph(3-NO₂) 1-144 Me Me H H SO₂CH₂ Ph(4-NO₂) 1-145 Me Me H H SO₂CH₂ Ph(2-CO₂Me) 97-98

TABLE 7 Melting point (° C.) or Compound refractive index No. R₁ R₂ R₃ R₄ Q Y (n_(D) ²⁰) 1-146 Me Me H H SO₂CH₂ Ph(3-CO₂Me) 1-147 Me Me H H SO₂CH₂ Ph(4-CO₂Me) 1-148 Me Me H H SO₂CH₂ Ph(2-NHSO₂Me) 1-149 Me Me H H SO₂CH₂ Ph(3-NHSO₂Me) 1-150 Me Me H H SO₂CH₂ Ph(4-NHSO₂Me) 1-151 Me Me H H SO₂CH₂ Ph(2-NHCH₂COMe) 1-152 Me Me H H SO₂CH₂ Ph(3-NHCH₂COMe) 1-153 Me Me H H SO₂CH₂ Ph(4-NHCH₂COMe) 1-154 Me Me H H SO₂CH₂ Ph(2-NHCH₂SO₂Me) 1-155 Me Me H H SO₂CH₂ Ph(3-NHCH₂SO₂Me) 1-156 Me Me H H SO₂CH₂ Ph(4-NHCH₂SO₂Me) 1-157 Me Me H H SO₂CH₂ Ph(2-CF₃) 1.5009 1-158 Me Me H H SO₂CH₂ Ph(3-CF₃) 103-104 1-159 Me Me H H SO₂CH₂ Ph(4-CF₃) 1-160 Me Me H H SO₂CH₂ Ph(2-CH₂OMe) 1.5352 1-161 Me Me H H SO₂CH₂ Ph(3-CH₂OMe) 1-162 Me Me H H SO₂CH₂ Ph(4-CH₂OMe) 1-163 Me Me H H SO₂CH₂ Ph(2-CH₂OH) 1-164 Me Me H H SO₂CH₂ Ph(3-CH₂OH) 1-165 Me Me H H SO₂CH₂ Ph(4-CH₂OH) 1-166 Me Me H H SO₂CH₂ Ph(2-CH₂SMe) 1-167 Me Me H H SO₂CH₂ Ph(3-CH₂SMe) 1-168 Me Me H H SO₂CH₂ Ph(4-CH₂SMe) 1-169 Me Me H H SO₂CH₂ Ph(2-CH₂SOMe) 1-170 Me Me H H SO₂CH₂ Ph(3-CH₂SOMe)

TABLE 8 Melting point (° C.) or Compound refractive index No. R₁ R₂ R₃ R₄ Q Y (n_(D) ²⁰) 1-171 Me Me H H SO₂CH₂ Ph(4-CH₂SOMe) 1-172 Me Me H H SO₂CH₂ Ph(2-CH₂SO₂Me) 1-173 Me Me H H SO₂CH₂ Ph(3-CH₂SO₂Me) 1-174 Me Me H H SO₂CH₂ Ph(4-CH₂SO₂Me) 1-175 Me Me H H SO₂CH₂ Ph(2-CH₂NHMe) 1-176 Me Me H H SO₂CH₂ Ph(3-CH₂NHMe) 1-177 Me Me H H SO₂CH₂ Ph(4-CH₂NHMe) 1-178 Me Me H H SO₂CH₂ Ph(2-CH₂N(Me)₂) 1-179 Me Me H H SO₂CH₂ Ph(3-CH₂N(Me)₂) 1-180 Me Me H H SO₂CH₂ Ph(4-CH₂N(Me)₂) 1-181 Me Me H H SO₂CH₂ Ph(2-CH₂CN) 1-182 Me Me H H SO₂CH₂ Ph(3-CH₂CN) 1-183 Me Me H H SO₂CH₂ Ph(4-CH₂CN) 1-184 Me Me H H SO₂CH₂ Ph(2-F, 3-Cl) 128-130 1-185 Me Me H H SO₂CH₂ Ph(2,6-Me₂) 110-112 1-186 Me Me H H SO₂CH₂ Ph(2-OEt, 3-Me) 1.5231 1-187 Me Me H H SO₂CH₂ Ph(2-F, 3-Me) 91-92 1-188 Me Et H H SO₂CH₂ Ph 38-39 1-189 Me Et H H SO₂CH₂ Ph(2-F) 65-67 1-190 Me Et H H SO₂CH₂ Ph(3-F) 58-59 1-191 Me Et H H SO₂CH₂ Ph(4-F) 75-78 1-192 Me Et H H SO₂CH₂ Ph(2-Cl) 1.5472 1-193 Me Et H H SO₂CH₂ Ph(3-Cl) 67-68 1-194 Me Et H H SO₂CH₂ Ph(4-Cl) 93-94 1-195 Me Et H H SO₂CH₂ Ph(2-Br) 1.5289

TABLE 9 Melting Com- point (° C.) or pound refractive index No. R₁ R₂ R₃ R₄ Q Y (n_(D) ²⁰) 1-196 Me Et H H SO₂CH₂ Ph(3-Br) 1-197 Me Et H H SO₂CH₂ Ph(4-Br) 1-198 Me Et H H SCH₂ Ph(2,6-F₂) 51-52 1-199 Me Et H H SOCH₂ Ph(2,6-F₂) <30 1-200 Me Et H H SO₂CH₂ Ph(2,6-F₂) 64-65 1-201 Me Et H H SO₂CH₂ Ph(2-Me) 1.5371 1-202 Me Et H H SO₂CH₂ Ph(3-Me) 41-42 1-203 Me Et H H SO₂CH₂ Ph(4-Me) 43-44 1-204 Me Et H H SO₂CH₂ Ph(2-Et) 1-205 Me Et H H SO₂CH₂ Ph(3-Et) 1-206 Me EL H H SO₂CH₂ Ph(4-Et) 1-207 Me Et H H SO₂CH₂ Ph(2-Pr) 1-208 Me Et H H SO₂CH₂ Ph(3-Pr) 1-209 Me Et H H SO₂CH₂ Ph(4-Pr) 1-210 Me Et H H SO₂CH₂ Ph(2-Pr-i) 1-211 Me Et H H SO₂CH₂ Ph(3-Pr-i) 1-212 Me Et H H SO₂CH₂ Ph(4-Pr-i) 1-213 Me Et H H SO₂CH₂ Ph(2-Bu) 1-214 Me Et H H SO₂CH₂ Ph(3-Bu) 1-215 Me Et H H SO₂CH₂ Ph(4-Bu) 1-216 Me Et H H SO₂CH₂ Ph(2-Bu-i) 1-217 Me Et H H SO₂CH₂ Ph(3-Bu-i) 1-218 Me Et H H SO₂CH₂ Ph(4-Bu-i) 1-219 Me Et H H SO₂CH₂ Ph(2-Bu-s) 1-220 Me Et H H SO₂CH₂ Ph(3-Bu-s)

TABLE 10 Melting Com- point (° C.) or pound refractive index No. R₁ R₂ R₃ R₄ Q Y (n_(D) ²⁰) 1-221 Me Et H H SO₂CH₂ Ph(4-Bu-s) 1-222 Me Et H H SO₂CH₂ Ph(2-Bu-t) 1-223 Me Et H H SO₂CH₂ Ph(3-Bu-t) 1-224 Me Et H H SO₂CH₂ Ph(4-Bu-t) 1-225 Me Et H H SO₂CH₂ Ph(2-Hex) 1-226 Me Et H H SO₂CH₂ Ph(3-Hex) 1-227 Me Et H H SO₂CH₂ Ph(4-Hex) 1-228 Me Et H H SO₂CH₂ Ph(2-OMe) Unable to measure 1-229 Me Et H H SO₂CH₂ Ph(3-OMe) 1.5219 1-230 Me Et H H SO₂CH₂ Ph(4-OMe) 72-74 1-231 Me Et H H SO₂CH₂ Ph(2-OEt) 1-232 Me Et H H SO₂CH₂ Ph(3-OEt) 1-233 Me Et H H SO₂CH₂ Ph(4-OEt) 1-234 Me Et H H SO₂CH₂ Ph(2-OPr) 1-235 Me Et H H SO₂CH₂ Ph(3-OPr) 1-236 Me Et H H SO₂CH₂ Ph(4-OPr) 1-237 Me Et H H SO₂CH₂ Ph(2-OPr-i) 1-238 Me Et H H SO₂CH₂ Ph(3-OPr-i) 1-239 Me Et H H SO₂CH₂ Ph(4-OPr-i) 1-240 Me Et H H SO₂CH₂ Ph(2-OHex) 1-241 Me Et H H SO₂CH₂ Ph(3-OHex) 1-242 Me Et H H SO₂CH₂ Ph(4-OHex) 1-243 Me Et H H SO₂CH₂ Ph(2-OCHF₂) 1-244 Me Et H H SO₂CH₂ Ph(3-OCHF₂) 1-245 Me Et H H SO₂CH₂ Ph(4-OCHF₂)

TABLE 11 Melting point (° C.) or Compound refractive index No. R₁ R₂ R₃ R₄ Q Y (n_(D) ²⁰) 1-246 Me Et H H SO₂CH₂ Ph(2-OCF₃) 1-247 Me Et H H SO₂CH₂ Ph(3-OCF₃) 1-248 Me Et H H SO₂CH₂ Ph(4-OCF₃) 1-249 Me Et H H SO₂CH₂ Ph(2-OCH₂CH₂OMe) 1-250 Me Et H H SO₂CH₂ Ph(3-OCH₂CH₂OMe) 1-251 Me Et H H SO₂CH₂ Ph(4-OCH₂CH₂OMe) 1-252 Me Et H H SO₂CH₂ Ph(2-SMe) 1-253 Me Et H H SO₂CH₂ Ph(3-SMe) 1-254 Me Et H H SO₂CH₂ Ph(4-SMe) 1-255 Me Et H H SO₂CH₂ Ph(2-SEt) 1-256 Me Et H H SO₂CH₂ Ph(3-SEt) 1-257 Me Et H H SO₂CH₂ Ph(4-SEt) 1-258 Me Et H H SO₂CH₂ Ph(2-SPr) 1-259 Me Et H H SO₂CH₂ Ph(3-SPr) 1-260 Me Et H H SO₂CH₂ Ph(4-SPr) 1-261 Me Et H H SO₂CH₂ Ph(2-SBu) 1-262 Me Et H H SO₂CH₂ Ph(3-SBu) 1-263 Me Et H H SO₂CH₂ Ph(4-SBu) 1-264 Me Et H H SO₂CH₂ Ph(2-SHex) 1-265 Me Et H H SO₂CH₂ Ph(3-SHex) 1-266 Me Et H H SO₂CH₂ Ph(4-SHex) 1-267 Me Et H H SO₂CH₂ Ph(2-SCHF₂) 1-268 Me Et H H SO₂CH₂ Ph(3-SCHF₂) 1-269 Me Et H H SO₂CH₂ Ph(4-SCHF₂) 1-270 Me Et H H SO₂CH₂ Ph(2-SCH₂CH₂OMe)

TABLE 12 Melting point (° C.) or Compound refractive index No. R₁ R₂ R₃ R₄ Q Y (n_(D) ²⁰) 1-271 Me Et H H SO₂CH₂ Ph(3-SCH₂CH₂OMe) 1-272 Me Et H H SO₂CH₂ Ph(4-SCH₂CH₂OMe) 1-273 Me Et H H SO₂CH₂ Ph(2-SOMe) 1-274 Me Et H H SO₂CH₂ Ph(3-SOMe) 1-275 Me Et H H SO₂CH₂ Ph(4-SOMe) 1-276 Me Et H H SO₂CH₂ Ph(2-SOEt) 1-277 Me Et H H SO₂CH₂ Ph(3-SOEt) 1-278 Me Et H H SO₂CH₂ Ph(4-SOEt) 1-279 Me Et H H SO₂CH₂ Ph(2-SOPr) 1-280 Me Et H H SO₂CH₂ Ph(3-SOPr) 1-281 Me Et H H SO₂CH₂ Ph(4-SOPr) 1-282 Me Et H H SO₂CH₂ Ph(2-SOBu) 1-283 Me Et H H SO₂CH₂ Ph(3-SOBu) 1-284 Me Et H H SO₂CH₂ Ph(4-SOBu) 1-285 Me Et H H SO₂CH₂ Ph(2-SOHex) 1-286 Me Et H H SO₂CH₂ Ph(3-SOHex) 1-287 Me Et H H SO₂CH₂ Ph(4-SOHex) 1-288 Me Et H H SO₂CH₂ Ph(2-SOCH₂CF₃) 1-289 Me Et H H SO₂CH₂ Ph(3-SOCH₂CF₃) 1-290 Me Et H H SO₂CH₂ Ph(4-SOCH₂CF₃) 1-291 Me Et H H SO₂CH₂ Ph(2-SOCH₂CH₂OMe) 1-292 Me Et H H SO₂CH₂ Ph(3-SOCH₂CH₂OMe) 1-293 Me Et H H SO₂CH₂ Ph(4-SOCH₂CH₂OMe) 1-294 Me Et H H SO₂CH₂ Ph(2-SO₂Me) 1-295 Me Et H H SO₂CH₂ Ph(3-SO₂Me)

TABLE 13 Melting point (° C.) or Compound refractive index No. R₁ R₂ R₃ R₄ Q Y (n_(D) ²⁰) 1-296 Me Et H H SO₂CH₂ Ph(4-SO₂Me) 1-297 Me Et H H SO₂CH₂ Ph(2-SO₂Et) 1-298 Me Et H H SO₂CH₂ Ph(3-SO₂Et) 1-299 Me Et H H SO₂CH₂ Ph(4-SO₂Et) 1-300 Me Et H H SO₂CH₂ Ph(2-SO₂Pr) 1-301 Me Et H H SO₂CH₂ Ph(3-SO₂Pr) 1-302 Me Et H H SO₂CH₂ Ph(4-SO₂Pr) 1-303 Me Et H H SO₂CH₂ Ph(2-SO₂Bu) 1-304 Me Et H H SO₂CH₂ Ph(3-SO₂Bu) 1-305 Me Et H H SO₂CH₂ Ph(4-SO₂Bu) 1-306 Me Et H H SO₂CH₂ Ph(2-SO₂Hex) 1-307 Me Et H H SO₂CH₂ Ph(3-SO₂Hex) 1-308 Me Et H H SO₂CH₂ Ph(4-SO₂Hex) 1-309 Me Et H H SO₂CH₂ Ph(2-SO₂CH₂CF₃) 1-310 Me Et H H SO₂CH₂ Ph(3-SO₂CH₂CF₃) 1-311 Me Et H H SO₂CH₂ Ph(4-SO₂CH₂CF₃) 1-312 Me Et H H SO₂CH₂ Ph(2-SO₂CH₂CH₂OMe) 1-313 Me Et H H SO₂CH₂ Ph(3-SO₂CH₂CH₂OMe) 1-314 Me Et H H SO₂CH₂ Ph(4-SO₂CH₂CH₂OMe) 1-315 Me Et H H SO₂CH₂ Ph(2-OBn) 1-316 Me Et H H SO₂CH₂ Ph(3-OBn) 1-317 Me Et H H SO₂CH₂ Ph(4-OBn) 1-318 Me Et H H SO₂CH₂ Ph(2-OBn(2-Cl)) 1-319 Me Et H H SO₂CH₂ Ph(2-OBn(3-Me)) 1-320 Me Et H H SO₂CH₂ Ph(2-OBn(4-OMe))

TABLE 14 Melting Com- point (° C.) or pound refractive index No. R₁ R₂ R₃ R₄ Q Y (n_(D) ²⁰) 1-321 Me Et H H SO₂CH₂ Ph(2-NHMe) 1-322 Me Et H H SO₂CH₂ Ph(3-NHMe) 1-323 Me Et H H SO₂CH₂ Ph(4-NHMe) 1-324 Me Et H H SO₂CH₂ Ph(2-N(Me)₂) 1-325 Me Et H H SO₂CH₂ Ph(3-N(Me)₂) 1-326 Me Et H H SO₂CH₂ Ph(4-N(Me)₂) 1-327 Me Et H H SO₂CH₂ Ph(2-CN) 1-328 Me Et H H SO₂CH₂ Ph(3-CN) 83-84 1-329 Me Et H H SO₂CH₂ Ph(4-CN) 87-89 1-330 Me Et H H SO₂CH₂ Ph(2-NO₂) 1-331 Me Et H H SO₂CH₂ Ph(3-NO₂) 115-117 1-332 Me Et H H SO₂CH₂ Ph(4-NO₂) 1-333 Me Et H H SO₂CH₂ Ph(2-CO₂Me) 1-334 Me Et H H SO₂CH₂ Ph(3-CO₂Me) 1.5152 1-335 Me Et H H SO₂CH₂ Ph(4-CO₂Me) 1-336 Me Et H H SO₂CH₂ Ph(2-CF₃) 1.5021 1-337 Me Et H H SO₂CH₂ Ph(3-CF₃) 1-338 Me Et H H SO₂CH₂ Ph(4-CF₃) 1-339 Me Et H H SO₂CH₂ Ph(2-CH₂OMe) 1-340 Me Et H H SO₂CH₂ Ph(3-CH₂OMe) 1-341 Me Et H H SO₂CH₂ Ph(4-CH₂OMe) 1-342 Me Et H H SO₂CH₂ Ph(2-CH₂OH) 1-343 Me Et H H SO₂CH₂ Ph(3-CH₂OH) 1-344 Me Et H H SO₂CH₂ Ph(4-CH₂OH) 1-345 Me Et H H SO₂CH₂ Ph(2-CH₂SMe)

TABLE 15 Melting point (° C.) or Compound refractive index No. R₁ R₂ R₃ R₄ Q Y (n_(D) ²⁰) 1-346 Me Et H H SO₂CH₂ Ph(3-CH₂SMe) 1-347 Me Et H H SO₂CH₂ Ph(4-CH₂SMe) 1-348 Me Et H H SO₂CH₂ Ph(2-CH₂SOMe) 1-349 Me Et H H SO₂CH₂ Ph(3-CH₂SOMe) 1-350 Me Et H H SO₂CH₂ Ph(4-CH₂SOMe) 1-351 Me Et H H SO₂CH₂ Ph(2-CH₂SO₂Me) 1-352 Me Et H H SO₂CH₂ Ph(3-CH₂SO₂Me) 1-353 Me Et H H SO₂CH₂ Ph(4-CH₂SO₂Me) 1-354 Me Et H H SO₂CH₂ Ph(2-CH₂NHMe) 1-355 Me Et H H SO₂CH₂ Ph(3-CH₂NHMe) 1-356 Me Et H H SO₂CH₂ Ph(4-CH₂NHMe) 1-357 Me Et H H SO₂CH₂ Ph(2-CH₂N(Me)₂) 1-358 Me Et H H SO₂CH₂ Ph(3-CH₂N(Me)₂) 1-359 Me Et H H SO₂CH₂ Ph(4-CH₂N(Me)₂) 1-360 Me Et H H SO₂CH₂ Ph(2-CH₂CN) 1-361 Me Et H H SO₂CH₂ Ph(3-CH₂CN) 1-362 Me Et H H SO₂CH₂ Ph(4-CH₂CN) 1-363 Et Et H H SOCH₂ Ph(2,6-F₂) 63-65 1-364 Et Et H H SO₂CH₂ Ph(2,6-F₂) 87-89 1-365 Me Pr H H SOCH2 Ph(2,6-F₂) 44-47 1-366 Me Pr H H SO₂CH₂ Ph(2,6-F₂) 61-63 1-367 Me Pr-i H H SOCH₂ Ph(2,6-F₂) 1.5319 1-368 Me Pr-i H H SO₂CH₂ Ph(2,6-F₂) 62-63 1-369 Me Me H H SO₂CH(Me) Ph 1-370 Me Me H H SO₂CH(Me) Ph(2,6-F₂)

TABLE 16 Melting point (° C.) or Compound refractive index No. R₁ R₂ R₃ R₄ Q Y (n_(D) ²⁰) 1-371 Me Et H H SO₂CH(Me) Ph 1-372 Me Et H H SO₂CH(Me) Ph(2,6-F₂) 1-373 Me Me H H SO₂C(Me)₂ Ph 1-374 Me Me H H SO₂C(Me)₂ Ph(2,6-F₂) 1-375 Me Et H H SO₂C(Me)₂ Ph 1-376 Me Et H H SO₂C(Me)₂ Ph(2,6-F₂) 1-377 Me Bn H H SO₂CH₂ Ph(2,6-F₂) 111-113 1-378 Me Pr-c H H SO₂CH₂ Ph(2,6-F₂) 49-51 1-379 Me CH₂Pr-c H H SO₂CH₂ Ph(2,6-F₂) 1-380 —(CH₂)₂— H H SO₂CH₂ Ph(2,6-F₂) 137-138 1-381 —(CH₂)₃— H H SCH₂ Ph(2,6-F₂) 93-95 1-382 —(CH₂)₃— H H SO₂CH₂ Ph(2,6-F₂)   115-115.5 1-383 —(CH₂)₄— H H SO₂CH₂ Ph(2,6-F₂) 113-114 1-384 —(CH₂)₅— H H SO₂CH₂ Ph(2,6-F₂) 118-120 1-385 H —(CH₂)₃— H SO₂CH₂ Ph(2,6-F₂) 1-386 H —(CH₂)₄— H SCH₂ Ph(2,6-F₂) 1.5529 1-387 H —(CH₂)₄— H SO₂CH₂ Ph(2,6-F₂) 1.5342 1-388 H —(CH₂)₅— H SO₂CH₂ Ph(2,6-F₂) 138-139 1-389 Me CH₂CO₂Me H H SO₂CH₂ Ph(2,6-F₂) 1-390 Me CH₂CO₂Et H H SO₂CH₂ Ph(2,6-F₂) 1.516 1-391 Me CH₂CN H H SO₂CH₂ Ph(2,6-F₂) 1-392 Me CH₂OH H H SCH₂ Ph(2,6-F₂) 73-75 1-393 Me CH₂OH H H SOCH₂ Ph(2,6-F₂) 80-84 1-394 Me CH₂OH H H SO₂CH₂ Ph(2,6-F₂) 129-131 1-395 Me CH₂OMe H H SCH₂ Ph(2,6-F₂) 1.5279

TABLE 17 Melting point (° C.) Compound or refractive No. R₁ R₂ R₃ R₄ Q Y index (n_(D) ²⁰) 1-396 Me CH₂OMe H H SOCH₂ Ph(2,6-F₂) 1.5293 1-397 Me CH₂OMe H H SO₂CH₂ Ph(2,6-F₂) 105-106 1-398 Me CH₂OPh(2,6-Cl₂) H H SCH₂ Ph(2,6-F₂) 1.5715 1-399 Me CH₂OPh(2,6-Cl₂) H H SOCH₂ Ph(2,6-F₂) 1.5674 1-400 Me CH₂OPh(2,6-Cl₂) H H SO₂CH₂ Ph(2,6-F₂) 1.5461 1-401 Me CH₂OBn(2,6-F₂) H H SO₂CH₂ Ph(2,6-F₂) 1.5257 1-402 Me CH₂SMe H H SO₂CH₂ Ph(2,6-F₂) 1-403 Me CH₂SEt H H SO₂CH₂ Ph(2,6-F₂) 1-404 Me CH₂SPr H H SO₂CH₂ Ph(2,6-F₂) 1-405 Me CH₂SPr-i H H SO₂CH₂ Ph(2,6-F₂) 1-406 Me CH₂SOMe H H SO₂CH₂ Ph(2,6-F₂) 1-407 Me CH₂SOEt H H SO₂CH₂ Ph(2,6-F₂) 1-408 Me CH₂SOPr H H SO₂CH₂ Ph(2,6-F₂) 1-409 Me CH₂SOPr-i H H SO₂CH₂ Ph(2,6-F₂) 1-410 Me CH₂NHMe H H SO₂CH₂ Ph(2,6-F₂) 1-411 Me CH₂NHEt H H SCH₂ Ph(2,6-F₂) 1.5268 1-412 Me CH₂NHEt H H SO₂CH₂ Ph(2,6-F₂) 1-413 Me CH₂NHPr H H SO₂CH₂ Ph(2,6-F₂) 1-414 Me CH₂NHPr-i H H SO₂CH₂ Ph(2,6-F₂) 1-415 Me CH₂N(Me)₂ H H SO₂CH₂ Ph(2,6-F₂) 1-416 Me Bn(2-Me) H H SO₂CH₂ Ph(2,6-F₂) 1-417 Me Bn(3-OMe) H H SO₂CH₂ Ph(2,6-F₂) 1-418 Me Bn(4-Cl) H H SO₂CH₂ Ph(2,6-F₂) 1-419 Me CO₂H H H SCH₂ Ph(2,6-F₂) 107-108 1-420 Me CO₂Me H H SCH₂ Ph(2,6-F₂) 75-76

TABLE 18 Melting point (° C.) Compound or refractive No. R₁ R₂ R₃ R₄ Q Y index (n_(D) ²⁰) 1-421 Me CO₂Me H H SOCH₂ Ph(2,6-F₂) 56-59 1-422 Me CO₂Me H H SO₂CH₂ Ph(2,6-F₂) 115-116 1-423 Me CO₂Et H H SO₂CH₂ Ph(2,6-F₂) 1-424 Me CO₂Pr H H SO₂CH₂ Ph(2,6-F₂) 1-425 Me CO₂Pr-i H H SO₂CH₂ Ph(2,6-F₂) 1-426 Me COSMe H H SO₂CH₂ Ph(2,6-F₂) 1-427 Me COSEt H H SO₂CH₂ Ph(2,6-F₂) 1-428 Me COSPr H H SO₂CH₂ Ph(2,6-F₂) 1-429 Me COSPr-i H H SO₂CH₂ Ph(2,6-F₂) 1-430 Me CONHMe H H SO₂CH₂ Ph(2,6-F₂) 1-431 Me CONHEt H H SO₂CH₂ Ph(2,6-F₂) 1-432 Me CONHPr H H SO₂CH₂ Ph(2,6-F₂) 1-433 Me CONHPr-i H H SO₂CH₂ Ph(2,6-F₂) 1-434 Me CON(Me)₂ H H SCH₂ Ph(2,6-F₂) 1.5423 1-435 Me CON(Me)₂ H H SOCH₂ Ph(2,6-F₂) 1.5409 1-436 Me CON(Me)₂ H H SO₂CH₂ Ph(2,6-F₂) 1.5236 1-437 Me CON(Et)(Me) H H SO₂CH₂ Ph(2,6-F₂) 1-438 Me CON(Et)₂ H H SO₂CH₂ Ph(2,6-F₂) 1-439 Me CON(Pr)₂ H H SO₂CH₂ Ph(2,6-F₂) 1-440 Me Ph H H SO₂CH₂ Ph(2,6-F₂) 1-441 Me Ph(2-Me) H H SO₂CH₂ Ph(2,6-F₂) 1-442 Me Ph(3-OMe) H H SO₂CH₂ Ph(2,6-F₂) 1-443 Me Ph(4-Cl) H H SOCH₂ Ph(2,6-F₂) 1.5788 1-444 Me Ph(4-Cl) H H SO₂CH₂ Ph(2,6-F₂) 100-101 1-445 Me Me Me Me SOCH₂ Ph(2,6-F₂)

TABLE 19 Melting point (° C.) Compound or refractive No. R₁ R₂ R₃ R₄ Q Y index (n_(D) ²⁰) 1-446 Me Me Me Me SO₂CH₂ Ph(2,6-F₂) 1-447 H H Me Me SOCH₂ Ph(2,6-F₂) 1-448 H H Me Me SO₂CH₂ Ph(2,6-F₂) 1-449 Me Me H H SO₂CH(CO₂Me) Ph(2,6-F₂) 1-450 Me Me H H SO₂CH(CN) Ph(2,6-F₂) 1-451 Me Me H H SO₂(CH₂)₂ Ph(2,6-F₂) 1-452 Me Me H H SO₂(CH₂)₃ Ph(2,6-F₂) 1-453 Me Et H H SO₂CH(CO₂Me) Ph(2,6-F₂) 1-454 Me Et H H SO₂CH(CN) Ph(2,6-F₂) 1-455 Me Et H H SO₂(CH₂)₂ Ph(2,6-F₂) 1-456 Me Et H H SO₂(CH₂)₂ Ph 63-64 1-457 Me Et H H SO₂(CH₂)₃ Ph 1.5161 1-458 Me Et H H SO₂(CH₂)₃ Ph(2,6-F₂) 1-459 Me Me H H SO₂CH₂ CF₃ 1-460 Me Me H H SO₂CH₂ CH₂CF₃ 1-461 Me Me H H SO₂CH₂ CH₂OH 1-462 Me Me H H SCH₂ CH₂OH 1-463 Me Me H H SO₂CH₂ CH₂OMe 1-464 Me Me H H SO₂CH₂ CH₂OHex 1-465 Me Me H H SO₂CH₂ CH₂OCH₂CH═CH₂ 1-466 Me Me H H SO₂CH₂ CH₂OBn 1-467 Me Et H H SCH₂ CO₂H 1.5088 1-468 Me Et H H SO₂CH₂ CH₂CO₂Me 1.4852 1-469 Me Et H H SCH₂ CH₂CO₂Me 1.4919 1-470 Me Me H H SO₂CH₂ CH₂CO₂Me

TABLE 20 Melting point (° C.) Compound or refractive No. R₁ R₂ R₃ R₄ Q Y index (n_(D) ²⁰) 1-471 Me Me H H SO₂CH₂ CH₂CO₂H 1-472 Me Me H H SO₂CH₂ CH₂OH 1-473 Me Me H H SO₂CH₂ CH₂CHO 1-474 Me Me H H SO₂CH₂ CH═CH₂ 1-475 Me Et H H SO₂CH₂ CF₃ 1-476 Me Et H H SO₂CH₂ CH₂CF₃ 1-477 Me Et H H SCH₂ CH₂OH 1.5088 1-478 Me Et H H SO₂CH₂ CH₂OH 1-479 Me Et H H SO₂CH₂ CH₂OMe 1-480 Me Et H H SO₂CH₂ CH₂OHex 1-481 Me Et H H SO₂CH₂ CH₂OCH₂CH═CH₂ 1-482 Me Et H H SO₂CH₂ CH₂OBn 1-483 Me Et H H SO₂CH₂ CH₂CO₂Me 1-484 Me Et H H SO₂CH₂ CH₂CO₂Hex 1-485 Me Et H H SO₂CH₂ CH₂OH 1-486 Me Et H H SO₂CH₂ CH₂CHO 1-487 Me Me H H SO₂CH₂ Ph(2,3-Cl₂) 128-129 1-488 Me Me H H SO₂CH₂ Ph(2,4-Cl₂) 122-123 1-489 Me Me H H SO₂CH₂ Ph(2,5-Cl₂) 123-124 1-490 Me Me H H SO₂CH₂ Ph(2,6-Cl₂) 153-154 1-491 Me Me H H SO₂CH₂ Ph(3,4-Cl₂) 121-122 1-492 Me Me H H SO₂CH₂ Ph(3,5-Cl₂) 103-104 1-493 Me —(CH₂)₄— H SO₂CH₂ Ph(2,6-F₂) 95-97 1-494 Me Me H H SO₂CH₂ Ph(2-Cl, 6-P) 108-109 1-495 Me Me Me H SO₂CH₂ Ph(2,6-F₂) 1.5183

TABLE 21 Melting point (° C.) Compound or refractive No. R₁ R₂ R₃ R₄ Q Y index (n_(D) ²⁰) 1-496 Me H Me H SO₂CH₂ Ph(2,6-F₂) 64-65 1-497 Me Me H H SO₂CH₂ Ph(3,4-F₂) 109-110 1-498 Me Me H H SO₂CH₂ Ph(2,5-F₂) 107-108 1-499 Me Me H H SO₂CH₂ Ph(2-F,6-NO₂) 146-147 1-500 Me Me H H SO₂CH₂ Ph(2,4,6-F3) 87-88 1-501 Me Me H H SO₂CH₂ Ph(2,3,6-F3) 136-138 1-502 Me Me H H SO₂CH₂ Ph(2,6-Et₂) 50-53 1-503 Me Me H H SO₂CH₂ Ph(2-NO₂, 3-CO₂Me) 112-114 1-504 Me Me H H SO₂CH₂ Ph(2,3-F₂) 124-125 1-505 Me Me H H SO₂CH₂ Ph(2,4-F₂) 104-105 1-506 Me Me H H SO₂CH₂ Ph(3,5-F₂) 139-140 1-507 Me Me H H SO₂CH₂ Ph(2,3,4-F₃) 100-103 1-508 Me Me H H SO₂CH₂ Ph(2,3,5-F₃) 105-107 1-509 Me Me H H SO₂CH₂ Ph(3,4,5-F₃) 150-151 1-510 Me Me H H SO₂CH₂ Ph(2,4,5-F₃) 121-126 1-511 Me Me H H SO₂CH₂ Ph(2,4-Me₂) 1.5421 1-512 Me Me H H SO₂CH₂ Ph(2,5-Me₂) 65-66 1-513 Me Me H H SO₂CH₂ Ph(3,4-Me₂) 62-65 1-514 Me Me H H SO₂CH₂ Ph(2-F, 5-CF₃) 95-97 1-515 Me Me H H SO₂CH₂ Ph(2-F, 3-CF₃) 109-111 1-516 Me Me H H SO₂CH₂ Ph(2-F, 4-Br) 123-125 1-517 Me Me H H SO₂CH₂ Ph(2-SO₂CF₃) 80-81 1-518 H —(CH₂)₅— H SO₂CH₂ Ph(2,6-F₂) 65-66 1-519 H —(CH₂)₆— H SO₂CH₂ Ph(2,6-F₂) 97-99 1-520 Pr-c Pr-c H H SO₂CH₂ Ph(2,6-F₂) 95-96

TABLE 22 Melting Com- point (° C.) pound or refractive No. R₁ R₂ R₃ R₄ Q Y index (n_(D) ²⁰) 1-521 Me Me H H SO₂CH₂ Ph(2-I) 70-72 1-522 Me Me H H SO₂CH₂ Ph(2,3-Me₂) 123-124 1-523 Me Me H H SO₂CH₂ Ph(3,5-Me₂) 97-98 1-524 Me Me H H SO₂CH₂ Ph(3,5-OMe₂) 125-126 1-525 Me Me H H SO₂CH₂ Ph(2-Et, 6-Me) 1.5414 1-526 Me Me H H SO₂CH₂ Ph(2-OEt, 6-F) 1.5251 1-527 Me Me H H SO₂CH₂ Ph(2-F, 6-CF₃) 69-90 1-528 Me Me H H SO₂CH₂ Ph(2-F, 4-CF₃) 124-125 1-529 Me Me H H SO₂CH₂ Ph(2,4,6-Me₃) 119-120 1-530 Me Me H H SO₂CH₂ Ph(2-OMe, 125-126 5-NO₂) 1-531 Me Me H H SO₂CH₂ Ph(2,3,4,5,6-F₂) 113-114 1-532 Me H H H SO₂CH₂ Ph(2,6-F₂) 126-127 1-533 H H H H SO₂CH₂ Ph(2,6-F₂) 125-126 1-534 Me Me H H SO₂CH₂ Ph(2-F, 6-OMe) 125-127 1-535 Me Me H H SO₂CH₂ Ph(2,6-OMe₂) 165-167 1-536 Me Me H H SO₂CH₂ Ph(2,6-OEt₂) 85-88 1-537 Me Me H H SO₂CH₂ Ph(2-Me, 3-NO₂) 109-111 1-538 Me Me H H SO₂CH₂ Ph(2-Cl, 4-F) 92-93 1-539 Me Me H H SO₂CH₂ Ph(4-Cl, 2-NO₂) 136-137 1-540 Me Me H H SO₂CH₂ Ph(5-Me, 2-NO₂) 124-125 1-541 Me Me H H SO₂CH₂ Ph(4-F, 3-CF₃)  99-101 1-542 Me Me H H SO₂CH₂ Ph(3-F, 5-CF₃) 87-89 1-543 Me Me H H SO₂CH₂ Ph(3,5-(CF₃)₂) 130-132 1-544 Me Me H H SO₂CH₂ Ph(2,5-(CF₂)₂) 100-103 1-545 Me Me H H SO₂CH₂ Ph(3,5-Br₂) 115-116

TABLE 23 Melting point (° C.) Compound or refractive No. R₁ R₂ R₃ R₄ Q Y index (n_(D) ²⁰) 1-546 Me Me H H SO₂CH₂ Ph(3,5-(NO₂)₂) 162-163 1-547 Me Me H H SO₂CH₂ Ph(2,3,5,6-(Me)₄) 128-130 1-548 Me Me H H SO₂CH₂ Ph(2-F, 6-I) 137-138 1-549 Me Me H H SO₂CH₂ Ph(2-NH₂, 6-F) 118-121 1-550 Me Me H H SO₂CH₂ Ph(2,6-F₂, 3-Me) 118-119 1-551 Me Me H H SO₂CH₂ Ph(4-F, 2-CF₃) 50-51 1-552 Me Me H H SO₂CH₂ Ph(2-NH₂) 107-109 1-553 Me Me H H SO₂CH₂ Ph(2-Pr, 6-F) 126-127 1-554 Me Me H H SO₂CH₂ Ph(2,6-Br₂) 158-160 1-555 Me Me H H SO₂CH₂ Ph(2-F, 6-CO₂Me) 103-105 1-556 Me —(CH₂)₅— H SO₂CH₂ Ph(2,6-F₂) 86-87 1-557 Me Me H H SO₂CH₂ Ph(2-F, 6-NMe₂) 108-110 1-558 Me Me H H SO₂CH₂ Ph(2-F, 6-NEt₂) 90-92 1-559 Me Me H H SO₂CH₂ Ph(2-OCH₂C≡CH) 110-113 1-560 Me Me H H SO₂CH₂ Ph(2-Cl, 6-Me)  98-100 1-561 Me Me H H SO₂CH₂ Ph(2-Cl, 6-OCHF₂) 83-84 1-562 Me Pr-c H H SO₂CH₂ Ph(2-OCHF₂) 1.5215 1-563 Me Me H H SO₂CH₂ Ph(2-Cl, 6-OMe) 128-129 1-564 Me Me H H SO₂CH₂ Ph(2-Cl, 6-OEt) 65-67 1-565 Me Me H H SO₂CH₂ Ph(2-Cl, 6-OPr-n) 66-68 1-566 Me Me H H SO₂CH₂ Ph(2-Cl, 6-OPr-i) 1.5402 1-567 Me Me H H SO₂CH₂ Ph(2-Cl, 6-OCH₂CF₃) 92-95 1-568 Me Me H H SO₂CH₂ Ph(2-OBu-n) 50-51 1-569 Me Me H H SO₂CH₂ Ph(2-F, 6-OPr-n)   74-76.5 1-570 Me Me H H SO₂CH₂ Ph(2-F, 6-OPr-i) 1.5139

TABLE 24 Melting point (° C.) Compound or refractive No. R₁ R₂ R₃ R₄ Q Y index (n_(D) ²⁰) 1-571 Me Me H H SO₂CH₂ Ph(2-F, 6-OBu-n) 74-75 1-572 Me Me H H SO₂CH₂ Ph(2-Cl, 6-OBu-i) 92-94 1-573 Me Me H H SO₂CH₂ Ph(2-F, 6-OCHF₂) 1.4961 1-574 Me Me H H SO₂CH₂ Ph(2-Cl, 6-OBu-n) 65-67 1-575 Me Me H H SO₂CH(Me) Ph(2-CF₃) 1.4965 1-576 Me Me H H SO₂CH₂ Ph(2-F, 6-OCH₂C≡CH) 102-105 1-577 Me Me H H SO₂CH₂ Pb(2-OCH₂CO₂Me) 110-111 1-578 Me Me H H SO₂CH₂ Ph(2-OCH₂CO₂Et) 92-93 1-579 Me Me H H SO₂CH₂ Ph(2-O(CH₂)₂OMe) 1.5089 1-580 Me Me H H SO₂CH₂ Ph(2-O(CH₂)₂OEt) 1.4991 1-581 Me Me H H SO₂CH(Me) Ph 120-121 1-582 Me Me H H SCH(Me) Ph 59-60 1-583 Me Me H H SO₂CH₂ Ph(2-Me, 6-MeO) 92-93 1-584 Me Me H H SO₂CH₂ Ph(2-Me, 3-Pr-i, 6-MeO) 108-109 1-585 Me Me H H SO₂CH₂ Ph(2-OEt.6-CF₃) 88-89 1-586 Me Me H H SO₂CH₂ Ph(2-CH₂OEt) 1.5318 1-587 Me Me H H SO₂CH₂ Ph(2-OCOMe) 87-89 1-588 Me Me H H SO₂CH₂ Ph(2-OCH₂Ph) 120-123 1-589 Me Me H H SO₂CH₂ Ph(2-OCH₂CH═CH₂) 71-73 1-590 Me Me H H SO₂CH₂ Ph(2-Cl, 6-OCH₂CH≡CH₂) Unable to measure 1-591 Me Me H H SO₂CH₂ Ph(2-Cl, 6-OCH₂C≡CH) 108-111 1-592 Me Me H H SO₂CH₂ Ph(2-CO₂H) 182-184 1-593 Me Me H H SO₂CH₂ Ph(2-CO₂Et) 1.5332 1-594 Me Me H H SO₂CH₂ Ph(2-CO₂Pr-n) 1.5294 1-595 Me Me H H SO₂CH₂ Ph(2-CO₂Pr-i) 1.5252

TABLE 25 Melting point (° C.) Compound or refractive No. R₁ R₂ R₃ R₄ Q Y index (n_(D) ²⁰) 1-596 Me Me H H SO₂CH₂ Ph(2-CO₂Bu-n) 1.5262 1-597 Me Me H H SO₂CH₂ Ph(2-CO₂Bu-s) 1.5223 1-598 Me Me H H SO₂CH₂ Ph(2-CO₂Bu-i) 64-65 1-599 Me Me H H SO₂CH₂ Ph(2-CO₂CH₂CH═CH₂) Unable to measure 1-600 Me Me H H SO₂CH₂ Ph(2-CO₂CH₂C≡CH) 90-91 1-601 Me Me H H SO₂CH₂ Ph(2-CO₂Pen-c) 78-79 1-602 Me Me H H SO₂CH₂ Ph(2-OEt, 6-Me) Unable to measure 1-603 Me Me H H SO₂CH₂ Ph(2-OPr-n, 6-Me) Unable to measure 1-604 Me Me H H SO₂CH₂ Ph(2-OPr-i, 6-Me) 1.5364 1-605 Me Me H H SO₂CH₂ Ph(2-OBu-n, 6-Me) Unable to measure 1-606 Me Me H H SO₂CH₂ Ph(2-Me, 6-OCH₂CH═CH₂) Unable to measure 1-607 Me Me H H SO₂CH₂ Ph(2-Me, 6-OCH₂C≡CH) Unable to measure 1-608 Me Me H H SO₂CH₂ Ph(2-OCH₂Pr-c) 1.5379 1-609 Me Me H H SO₂CH₂ Ph(2-OPen-c) 1.5409 1-610 Me Me H H SO₂CH₂ Ph(2-OHex-c) 1.5399 1-611 Me Me H H SO₂CH₂ Ph(2-CO₂CH₂Ph) 96-97 1-612 Me Me H H SO₂CH₂ Ph(2-CO₂CH₂Ph(2-Cl)) 1.5631 1-613 Me Me H H SO₂CH₂ Ph(2-CO₂CH₂Ph(3-Cl)) 1.5661 1-614 Me Me H H SO₂CH₂ Ph(2-CO₂CH₂Ph(4-Cl)) 1.5642 1-615 Me Me H H SO₂CH₂ Ph(2-CH₂OBu-n) 42-43 1-616 Me Me H H SO₂CH₂ Ph(2,3,6-Me₃) 97-99 1-617 Me Et H H SO₂CH₂ Ph(2,3,6-Me₃) 68-70 1-618 Me Me H H SO₂CH₂ Ph(2-Cl, 6-CO₂Me) 136-137 1-619 Me Me H H SO₂CH₂ Ph(2-Cl, 6-CO₂Et) 108-109 1-620 Me Me H H SO₂CH₂ Ph(2-Cl, 6-CO₂Pr-n) 76-77

TABLE 26 Melting point (° C.) Compound or refractive No. R₁ R₂ R₃ R₄ Q Y index (n_(D) ²⁰) 1-621 Me Me H H SO₂CH₂ Ph(2-Cl, 6-CO₂Pr-i) 114-115 1-622 Me Me H H SO₂CH₂ Ph(2-Cl, 6-CO₂Bu-n) 94-95 1-623 Me Me H H SO₂CH₂ Ph(2-Cl, 6-CO₂Bu-s) 94-97 1-624 Me Me H H SO₂CH₂ Ph(2-Cl, 6-CO₂Bu-i)  99-100 1-625 Me Me H H SO₂CH₂ Ph(2-Cl, 6-CO₂CH₂Ph) 121-122 1-626 Me Me H H SO₂CH₂ Ph(2-Cl, 6-CO₂CH₂Ph(2-Cl)) 111-112 1-627 Me Me H H SO₂CH₂ Ph(2-Cl, 6-CO₂CH₂Ph(3-Cl)) 82-83 1-628 Me Me H H SO₂CH₂ Ph(2-Cl, 6-CO₂CH₂Ph(4-Cl)) 111-112 1-629 H CON(Et)₂ H H SCH₂ Ph(2,6-F₂) 1.5372 1-630 H CON(Et)₂ H H SOCH₂ Ph(2,6-F₂) 1.5374 1-631 H CON(Et)₂ H H SO₂CH₂ Ph(2,6-F₂) 1.5122 1-632 Me Me H H SO₂CH₂ Ph(2-Cl, 5-OMe) 92-93 1-633 Me Me H H SO₂CH₂ Ph(2-Cl, 5-OEt) 114-115 1-634 Me Me H H SO₂CH₂ Ph(2-Cl, 5-OPr-n) 95-96 1-635 Me Me H H SO₂CH₂ Ph(2-Cl, 5-OPr-i) 64-65 1-636 Me Me H H SO₂CH₂ Ph(2-Cl, 5-OBu-n) 87-88 1-637 Me Me H H SO₂CH₂ Ph(2-Cl, 5-OCH₂CH═CH₂) 66-67 1-638 Me Me H H SO₂CH₂ Ph(2-Cl, 5-OCH₂C≡CH) 91-92 1-639 Me Me H H SO₂CH₂ Ph(2-Et, 6-OMe) 78-79 1-640 Me Me H H SO₂CH₂ Ph(2-Cl, 6-CO₂H)   176-176.5 1-641 Me Me H H SO₂CH₂ Ph(2-F, 6-CO₂H) 176-177 1-642 Me Me H H SO₂CH₂ Ph(2-F, 6-CO₂Et) 67-68 1-643 Me Me H H SO₂CH₂ Ph(2-F, 6-CO₂Pr-n) 55-56 1-644 Me Me H H SO₂CH₂ Ph(2-F, 6-CO₂Pr-i) 92-93 1-645 Me Me H H SO₂CH₂ Ph(2-F, 6-CO₂Bu-n) 94-95

TABLE 27 Melting point (° C.) Compound or refractive No. R₁ R₂ R₃ R₄ Q Y index (n_(D) ²⁰) 1-646 Me Me H H SO₂CH₂ Ph(2-F, 6-CO₂Bu-s) 49-50 1-647 Me Me H H SO₂CH₂ Ph(2-F, 6-CO₂Bu-i) 86-87 1-648 Me Me H H SO₂CH₂ Ph(2-F, 6-CO₂CH₂Ph) 191-192 1-649 Me Me H H SO₂CH₂ Ph(2-F, 6-CO₂CH₂Ph(2-Cl)) 89-90 1-650 Me Me H H SO₂CH₂ Ph(2-F, 6-CO₂CH₂Ph(3-Cl)) 89-90 1-651 Me Me H H SO₂CH₂ Ph(2-F, 6-CO₂CH₂Ph(4-Cl)) 108-109 1-652 Me Et H H SO₂CH₂ Ph(2,3,5,6-(Me)₄) 94-95 1-653 Me Me H H SO₂CH₂ Ph(2-OEt, 6-Et) 88-90 1-654 Me Me H H SO₂CH₂ Ph(2-OPr-n, 6-Et) 1.5321 1-655 Me Me H H SO₂CH₂ Ph(2-OPr-i, 6-Et) 1.5312 1-656 Me Me H H SO₂CH₂ Ph(2-OBu-n, 6-Et) 43-45 1-657 Me Me H H SO₂CH₂ Ph(2-OCH₂CH═CH₂, 6-Et) 1.545  1-658 Me Me H H SO₂CH₂ Ph(2-OCH₂C≡CH, 6-Et) 1.5489 1-659 Me Me H H SO₂CH₂ Ph(2,3,5,6-F₄) 129-131 1-660 Me Et H H SO₂CH₂ Ph(2,3,5,6-F₄) 110-112 1-661 Me Me H H SO₂CH₂ Ph(2-CO₂Me, 3-Me) 1-662 Me Et H H SO₂CH₂ Ph(2-CO₂Me, 3-Me) 59-61 1-663 Me Me H H SO₂CH₂ Ph(2-CO₂Et, 3-Me) 1-664 Me Et H H SO₂CH₂ Ph(2-CO₂Et, 3-Me) 1.5292 1-665 Me Me H H SO₂CH₂ Ph(2-CO₂Bu-i, 3-Me) 1-666 Me Et H H SO₂CH₂ Ph(2-CO₂Bu-i, 3-Me) 1.5192 1-667 Me Me H H SO₂CH₂ Ph(2,5-Me₂, 6-OMe) 117-118 1-668 Me Me H H SO₂CH₂ Ph(2,5-Me₂, 6-OEt) 1.5309 1-669 Me Me H H SO₂CH₂ Ph(2,5-Me₂, 6-OPr-n) 75-76 1-670 Me Et H H SO₂CH₂ Ph(2,3,5,6-(Me)₄)

TABLE 28 Melting point (° C.) Compound or refractive No. R₁ R₂ R₃ R₄ Q Y index (n_(D) ²⁰) 1-671 Me Me H H SO₂CH₂ Ph(2,3,5-(Me)₃, 6-OMe) 1-672 Me Me H H SO₂CH₂ Ph(2,3,5-(Me)₃, 6-OEt) 1-673 Me Me H H SO₂CH₂ Ph(2,3,5-(Me)₃, 6-OPr-n) 1-674 Me Me H H SO₂CH₂ Ph(2,3,5-(Me)₃, 6-OPr-i) 1-675 Me Me H H SO₂CH₂ Ph(2,5-(Me)₂, 3,6-Cl₂) 1-676 Me Me H H SO₂CH₂ Ph(2,5-(Me)₂, 3,6-Br₂) 1-677 Me Me H H SO₂CH₂ Ph(2,3,6-(Me)₂, 5-Cl) 1-678 Me Me H H SO₂CH₂ Ph(2,3,6-(Me)₃, 5-Br) 1-679 Me Me H H SCH₂ Ph 1.5521 1-680 Me CH₂CO₂H H H SO₂CH₂ Ph(2,6-F₂) 1-681 Me CH₂COEt H H SO₂CH₂ Ph(2,6-F₂) 1-682 Me CH₂COMe H H SO₂CH₂ Ph(2,6-F₂) 1-683 Me CH₂CON(Et)₂ H H SO₂CH₂ Ph(2,6-F₂) 1-684 Me CH₂CON(Me)₂ H H SO₂CH₂ Ph(2,6-F₂) 1-685 Me CH₂CONHEt H H SO₂CH₂ Ph(2,6-F₂) 1-686 Me CH₂CONHMe H H SO₂CH₂ Ph(2,6-F₂) 1-687 Me CH₂COSEt H H SO₂CH₂ Ph(2,6-F₂) 1-688 Me CH₂COSMe H H SO₂CH₂ Ph(2,6-F₂) 1-689 Me CH₂OPh H H SO₂CH₂ Ph(2,6-F₂) 1-690 Me CH₂OPh(2-Me) H H SO₂CH₂ Ph(2,6-F₂) 1-691 Me CH₂OPh(2-OMe) H H SO₂CH₂ Ph(2,6-F₂) 1-692 Me CH₂OPh(3-Me) H H SO₂CH₂ Ph(2,6-F₂) 1-693 Me CH₂OPh(3-OMe) H H SO₂CH₂ Ph(2,6-F₂) 1-694 Me CH₂OPh(4-Me) H H SO₂CH₂ Ph(2,6-F₂) 1-695 Me CH₂OPh(4-OMe) H H SO₂CH₂ Ph(2,6-F₂)

TABLE 29 Melting point (° C.) Compound or refractive No. R₁ R₂ R₃ R₄ Q Y index (n_(D) ²⁰) 1-696 Me CH₂SO₂Et H H SO₂CH₂ Ph(2,6-F₂) 1-697 Me CH₂SO₂Me H H SO₂CH₂ Ph(2,6-F₂) 1-698 Me Et H H SCH₂ Ph(2,3,4,5,6-(Me)₅) 1-699 Me Et H H SCH₂ Ph(2,3,5-(Me)₃) 1-700 Me Et H H SCH₂ Ph(2,3,5-(Me)₃, 6-OCH₂CF₃) 1-701 Me Et H H SCH₂ Ph(2,3,5-(Me)₃, 6-OCHF₂) 1-702 Me Et H H SCH₂ Ph(2,3,5-(Me)₃, 6-OEt) 1-703 Me Et H H SCH₂ Ph(213,5-(Me)₃, 6-OMe) 1-704 Me Et H H SCH₂ Ph(2,3,5-(Me)₃, 6-OPr-i) 1-705 Me Et H H SCH₂ Ph(2,3,5-(Me)₃, 6-OPr-n) 1-706 Me Et H H SCH₂ Ph(213,6-(Me)₃, 5-Br) 1-707 Me Et H H SCH₂ Ph(2,3,6-(Me)₃, 5-Cl) 1-708 Me Et H H SCH₂ Ph(2,3,6-(Me)₃, 5-F) 1-709 Me Et H H SCH₂ Ph(2,3,6-(Me)₃, 5-I) 1-710 Me Et H H SCH₂ Ph(2,5-(Me)₂, 3,6-Br₂) 1-711 Me Et H H SCH₂ Ph(2,5-(Me)₃, 3,6-Cl₂) 1-712 Me Et H H SO₂CH₂ Ph(2,3,4,5,6-(Me)₅) 1-713 Me Et H H SO₂CH₂ Ph(2,3,5-(Me)₃) 1-714 Me Et H H SO₂CH₂ Ph(2,3,5-(Me)₃, 6-OCH₂CF₃) 1-715 Me Et H H SO₂CH₂ Ph(2,3,5-(Me)₃, 6-OCHF₂) 1-716 Me Et H H SO₂CH₂ Ph(2,3,5-(Me)₃, 6-OEt) 1-717 Me Et H H SO₂CH₂ Ph(2,3,5-(Me)₃, 6-OMe) 1-718 Me Et H H SO₂CH₂ Ph(2,3,5-(Me)₃, 6-OPr-i) 1-719 Me Et H H SO₂CH₂ Ph(2,3,5-(Me)₃, 6-OPr-n) 1-720 Me Et H H SO₂CH₂ Ph(2,3,6-(Me)₃, 5-Br)

TABLE 30 Melting point (° C.) Compound or refractive No. R₁ R₂ R₃ R₄ Q Y index (n_(D) ²⁰) 1-721 Me Et H H SO₂CH₂ Ph(2,3,6-(Me)₃, 5-Cl) 1-722 Me Et H H SO₂CH₂ Ph(2,3,6-(Me)₃, 5-F) 1-723 Me Et H H SO₂CH₂ Ph (2,3,6-(Me)₃, ,5-I) 1-724 Me Et H H SO₂CH₂ Ph(2,5-(Me)₂, 3,6-Br₂) 1-725 Me Et H H SO₂CH₂ Ph (2,5-(Me)₂, 3,6-Cl₂) 1-726 Me Et H H SOCH₂ Ph(2,3,4,5,6-(Me)₅) 1-727 Me Et H H SOCH₂ Ph(2,3,5-(Me)₃) 1-728 Me Et H H SOCH₂ Ph(2,3,5-(Me)₃, 6-OCH₂CF₃) 1-729 Me Et H H SOCH₂ Ph(2,3,5-(Me)₃, 6-OCHF₂) 1-730 Me Et H H SOCH₂ Ph(2,3,5-(Me)₃, 6-OEt) 1-731 Me Et H H SOCH₂ Ph(2,3,5-(Me)₃, 6-OMe) 1-732 Me Et H H SOCH₂ Ph(2,3,5-(Me)₃, 6-OPr-i) 1-733 Me Et H H SOCH₂ Ph(2,3,5-(Me)₃, 6-OPr-n) 1-734 Me Et H H SOCH₂ Ph(2,3,6-(Me)₃, 5-Br) 1-735 Me Et H H SOCH₂ Ph(2,3,6-(Me)₃, 5-Cl) 1-736 Me Et H H SOCH₂ Ph(2,3,6-(Me)₃, 5-F) 1-737 Me Et H H SOCH₂ Ph(2,3,6-(Me)₃, 5-I) 1-738 Me Et H H SOCH₂ Ph(2,5-(Me)₂, 3,6-Br₂) 1-739 Me Et H H SOCH₂ Ph(2,5-(Me)₂, 3,6-Cl₂) 1-740 Me Me H H SCH₂ Ph(2,3,4,5,6-(Me)₅) 1-741 Me Me H H SCH₂ Ph(2,3,5-(Me)₃) 1-742 Me Me H H SCH₂ Ph(2,3,5-(Me)₃, 6-OCH₂CF₃) 1-743 Me Me H H SCH₂ Ph(2,3,5-(Me)₃, 6-OCHF₂) 1-744 Me Me H H SCH₂ Ph(2,3,5-(Me)₃, 6-OEt) 1-745 Me Me H H SCH₂ Ph(2,3,5-(Me)₃, 6-OMe)

TABLE 31 Melting Com- point (° C.) pound or refractive No. R₁ R₂ R₃ R₄ Q Y index (n_(D) ²⁰) 1-746 Me Me H H SCH₂ Ph(2,3,5-(Me)₃, 6-OPr-i) 1-747 Me Me H H SCH₂ Ph(2,3,5-(Me)₃, 6-OPr-n) 1-748 Me Me H H SCH₂ Ph(2,3,5,6-(Me)₄) 1-749 Me Me H H SCH₂ Ph(2,3,6-(Me)₃, 5-Br) 1-750 Me Me H H SCH₂ Ph(2,3,6-(Me)₃, 5-Cl) 1-751 Me Me H H SCH₂ Ph(2,3,6-(Me)₃, 5-F) 1-752 Me Me H H SCH₂ Ph(2,3,6-(Me)₃, 5-I) 1-753 Me Me H H SCH₂ Ph(2,3-Me₂) 1-754 Me Me H H SCH₂ Ph(2,4-Me₂) 1-755 Me Me H H SCH₂ Ph(2,5-(Me)₂, 3,6-Br₂) 1-756 Me Me H H SCH₂ Ph(2,5-(Me)₂, 3,6-Cl₂) 1-757 Me Me H H SCH₂ Ph(2,5-Me₂) 1-758 Me Me H H SCH₂ Ph(2,6-Me₂) 1-759 Me Me H H SCH₂ Ph(2-Br) 1-760 Me Me H H SCH₂ Ph(2-Bu) 1-761 Me Me H H SCH₂ Ph(2-Bu-i) 1-762 Me Me H H SCH₂ Ph(2-Bu-s) 1-763 Me Me H H SCH₂ Ph(2-Bu-t) 1-764 Me Me H H SCH₂ Ph(2-CF₃) 1-765 Me Me H H SCH₂ Ph(2-Cl) 1-766 Me Me H H SCH₂ Ph(2-Et) 1-767 Me Me H H SCH₂ Ph(2-F) 1-768 Me Me H H SCH₂ Ph(2-Hex) 1-769 Me Me H H SCH₂ Ph(2-Me) 1-770 Me Me H H SCH₂ Ph(2-OCF₃)

TABLE 32 Melting point (° C.) Compound or refractive No. R₁ R₂ R₃ R₄ Q Y index (n_(D) ²⁰) 1-771 Me Me H H SCH₂ Ph(2-OCHF₂) 1-772 Me Me H H SCH₂ Ph(2-OEt) 1-773 Me Me H H SCH₂ Ph(2-OHex) 1-774 Me Me H H SCH₂ Ph(2-OMe) 1-775 Me Me H H SCH₂ Ph(2-OPr) 1-776 Me Me H H SCH₂ Ph(2-OPr-i) 1-777 Me Me H H SCH₂ Ph(2-Pr) 1-778 Me Me H H SCH₂ Ph(2-Pr-i) 1-779 Me Me H H SCH₂ Ph(3,4-Me₂) 1-780 Me Me H H SCH₂ Ph(3,5-Me₂) 1-781 Me Me H H SCH₂ Ph(3-Br) 1-782 Me Me H H SCH₂ Ph(3-Bu) 1-783 Me Me H H SCH₂ Ph(3-Bu-i) 1-784 Me Me H H SCH₂ Ph(3-Bu-s) 1-785 Me Me H H SCH₂ Ph(3-Bu-t) 1-786 Me Me H H SCH₂ Ph(3-CF₃) 1-787 Me Me H H SCH₂ Ph(3-Cl) 1-788 Me Me H H SCH₂ Ph(3-Et) 1-789 Me Me H H SCH₂ Ph(3-F) 1-790 Me Me H H SCH₂ Ph(3-Hex) 1-791 Me Me H H SCH₂ Ph(3-Me) 1-792 Me Me H H SCH₂ Ph(3-OCF₃) 1-793 Me Me H H SCH₂ Ph(3-OCHF₂) 1-794 Me Me H H SCH₂ Ph(3-OEt) 1-795 Me Me H H SCH₂ Ph(3-OHex)

TABLE 33 Melting point (° C.) Compound or refractive No. R₁ R₂ R₃ R₄ Q Y index (n_(D) ²⁰) 1-796 Me Me H H SCH₂ Ph(3-OMe) 1-797 Me Me H H SCH₂ Ph(3-OPr) 1-798 Me Me H H SCH₂ Ph(3-OPr-i) 1-799 Me Me H H SCH₂ Ph(3-Pr) 1-800 Me Me H H SCH₂ Ph(3-Pr-i) 1-801 Me Me H H SCH₂ Ph(4-Br) 1-802 Me Me H H SCH₂ Ph(4-Bu) 1-803 Me Me H H SCH₂ Ph(4-Bu-i) 1-804 Me Me H H SCH₂ Ph(4-Bu-s) 1-805 Me Me H H SCH₂ Ph(4-Bu-t) 1-806 Me Me H H SCH₂ Ph(4-CF₃) 1-807 Me Me H H SCH₂ Ph(4-Cl) 1-808 Me Me H H SCH₂ Ph(4-Et) 1-809 Me Me H H SCH₂ Ph(4-F) 1-810 Me Me H H SCH₂ Ph(4-Hex) 1-811 Me Me H H SCH₂ Ph(4-Me) 1-812 Me Me H H SCH₂ Ph(4-OCF₃) 1-813 Me Me H H SCH₂ Ph(4-OCHF₂) 1-814 Me Me H H SCH₂ Ph(4-OEt) 1-815 Me Me H H SCH₂ Ph(4-OHex) 1-816 Me Me H H SCH₂ Ph(4-OMe) 1-817 Me Me H H SCH₂ Ph(4-OPr) 1-818 Me Me H H SCH₂ Ph(4-OPr-i) 1-819 Me Me H H SCH₂ Ph(4-Pr) 1-820 Me Me H H SCH₂ Ph(4-Pr-i)

TABLE 34 Melting point (° C.) or Com- refractive pound index No. R₁ R₂ R₃ R₄ Q Y (n_(D) ²⁰) 1-821 Me Me H H SO₂CH₂ Ph(2,3,4,5,6-(Me)₅) 1-822 Me Me H H SO₂CH₂ Ph(2,3,5-(Me)₃) 1-823 Me Me H H SO₂CH₂ Ph(2,3,5-(Me)₃, 6-OCH₂CF₃) 1-824 Me Me H H SO₂CH₂ Ph(2,3,5-(Me)₃, 6-OCHF₂) 1-825 Me Me H H SO₂CH₂ Ph(2,3,6-(Me)₃, 5-F) 1-826 Me Me H H SO₂CH₂ Ph(2,3,6-(Me)₃, 5-I) 1-827 Me Me H H SOCH₂ Ph(2,3,4,5,6-(Me)₅) 1-828 Me Me H H SOCH₂ Ph(2,3,5-(Me)₃) 1-829 Me Me H H SOCH₂ Ph(2,3,5-(Me)₃, 6-OCH₂CF₃) 1-830 Me Me H H SOCH₂ Ph(2,3,5-(Me)₃, 6-OCHF₂) 1-831 Me Me H H SOCH₂ Ph(2,3,5-(Me)₃, 6-OEt) 1-832 Me Me H H SOCH₂ Ph(2,3,5-(Me)₃, 6-OMe) 1-833 Me Me H H SOCH₂ Ph(2,3,5-(Me)₃, 6-OPr-i) 1-834 Me Me H H SOCH₂ Ph(2,3,5-(Me)₃, 6-OPr-n) 1-835 Me Me H H SOCH₂ Ph(2,3,5,6-(Me)₄) 1-836 Me Me H H SOCH₂ Ph(2,3,6-(Me)₃, 5-Br) 1-837 Me Me H H SOCH₂ Ph(2,3,6-(Me)₃, 5-Cl) 1-838 Me Me H H SOCH₂ Ph(2,3,6-(Me)₃, 5-F) 1-839 Me Me H H SOCH₂ Ph(2,3,6-(Me)₃, 5-I) 1-840 Me Me H H SOCH₂ Ph(2,3-Me₂) 1-841 Me Me H H SOCH₂ Ph(2,4-Me₂) 1-842 Me Me H H SOCH₂ Ph(2,5-(Me)₂, 3,6-Br₂) 1-843 Me Me H H SOCH₂ Ph(2,5-(Me)₂, 3,6-Cl₂) 1-844 Me Me H H SOCH₂ Ph(2,5-Me₂) 1-845 Me Me H H SOCH₂ Ph(2,6-Me₂)

TABLE 35 Melting point (° C.) Compound or refractive No. R₁ R₂ R₃ R₄ Q Y index (n_(D) ²⁰) 1-846 Me Me H H SOCH₂ Ph(2-Br) 1-847 Me Me H H SOCH₂ Ph(2-Bu) 1-848 Me Me H H SOCH₂ Ph(2-Bu-i) 1-849 Me Me H H SOCH₂ Ph(2-Bu-s) 1-850 Me Me H H SOCH₂ Ph(2-Bu-t) 1-851 Me Me H H SOCH₂ Ph(2-CF₃) 1-852 Me Me H H SOCH₂ Ph(2-Cl) 1-853 Me Me H H SOCH₂ Ph(2-Et) 1-854 Me Me H H SOCH₂ Ph(2-F) 1-855 Me Me H H SOCH₂ Ph(2-Hex) 1-856 Me Me H H SOCH₂ Ph(2-Me) 1-857 Me Me H H SOCH₂ Ph(2-OCF₃) 1-858 Me Me H H SOCH₂ Ph(2-OCHF₂) 1-859 Me Me H H SOCH₂ Ph(2-OEt) 1-860 Me Me H H SOCH₂ Ph(2-OHex) 1-861 Me Me H H SOCH₂ Ph(2-OMe) 1-862 Me Me H H SOCH₂ Ph(2-OPr) 1-863 Me Me H H SOCH₂ Ph(2-OPr-i) 1-864 Me Me H H SOCH₂ Ph(2-Pr) 1-865 Me Me H H SOCH₂ Ph(2-Pr-i) 1-866 Me Me H H SOCH₂ Ph(3,4-Me₂) 1-867 Me Me H H SOCH₂ Ph(3,5-Me₂) 1-868 Me Me H H SOCH₂ Ph(3-Br) 1-869 Me Me H H SOCH₂ Ph(3-Bu) 1-870 Me Me H H SOCH₂ Ph(3-Bu-i)

TABLE 36 Melting point (° C.) Compound or refractive No. R₁ R₂ R₃ R₄ Q Y index (n_(D) ²⁰) 1-871 Me Me H H SOCH₂ Ph(3-Bu-s) 1-872 Me Me H H SOCH₂ Ph(3-Bu-t) 1-873 Me Me H H SOCH₂ Ph(3-CF₃) 1-874 Me Me H H SOCH₂ Ph(3-Cl) 1-875 Me Me H H SOCH₂ Ph(3-Et) 1-876 Me Me H H SOCH₂ Ph(3-F) 1-877 Me Me H H SOCH₂ Ph(3-Hex) 1-878 Me Me H H SOCH₂ Ph(3-Me) 1-879 Me Me H H SOCH₂ Ph(3-OCF₃) 1-880 Me Me H H SOCH₂ Ph(3-OCHF₂) 1-881 Me Me H H SOCH₂ Ph(3-OEt) 1-882 Me Me H H SOCH₂ Ph(3-OHex) 1-883 Me Me H H SOCH₂ Ph(3-OMe) 1-884 Me Me H H SOCH₂ Ph(3-OPr) 1-885 Me Me H H SOCH₂ Ph(3-OPr-i) 1-886 Me Me H H SOCH₂ Ph(3-Pr) 1-887 Me Me H H SOCH₂ Ph(3-Pr-i) 1-888 Me Me H H SOCH₂ Ph(4-Br) 1-889 Me Me H H SOCH₂ Ph(4-Bu) 1-890 Me Me H H SOCH₂ Ph(4-Bu-i) 1-891 Me Me H H SOCH₂ Ph(4-Bu-s) 1-892 Me Me H H SOCH₂ Ph(4-Bu-t) 1-893 Me Me H H SOCH₂ Ph(4-CF₃) 1-894 Me Me H H SOCH₂ Ph(4-Cl) 1-895 Me Me H H SOCH₂ Ph(4-Et)

TABLE 37 Melting point (° C.) Compound or refractive No. R₁ R₂ R₃ R₄ Q Y index (n_(D) ²⁰) 1-896 Me Me H H SOCH₂ Ph(4-F) 1-897 Me Me H H SOCH₂ Ph(4-Hex) 1-898 Me Me H H SOCH₂ Ph(4-Me) 1-899 Me Me H H SOCH₂ Ph(4-OCF₃) 1-900 Me Me H H SOCH₂ Ph(4-OCHF₂) 1-901 Me Me H H SOCH₂ Ph(4-OEt) 1-902 Me Me H H SOCH₂ Ph(4-OHex) 1-903 Me Me H H SOCH₂ Ph(4-OMe) 1-904 Me Me H H SOCH₂ Ph(4-OPr) 1-905 Me Me H H SOCH₂ Ph(4-OPr-i) 1-906 Me Me H H SOCH₂ Ph(4-Pr) 1-907 Me Me H H SOCH₂ Ph(4-Pr-i) 1-908 Me Me H CH₂Pr-c SO₂CH₂ Ph(2,6-F₂) 1-909 Me Me H CH₂CF₃ SO₂CH₂ Ph(2,6-F₂) 1-910 Me Me H CH₂OMe SO₂CH₂ Ph(2,6-F₂) 1-911 Me Me H CH₂Pr-c SOCH₂ Ph(2,6-F₂) 1-912 Me Me H CH₂CF₃ SOCH₂ Ph(2,6-F₂) 1-913 Me Me H CH₂OMe SOCH₂ Ph(2,6-F₂) 1-914 Me Me H CH₂Pr-c SCH₂ Ph(2,6-F₂) 1-915 Me Me H CH₂CF₃ SCH₂ Ph(2,6-F₂) 1-916 Me Me H CH₂OMe SCH₂ Ph(2,6-F₂) 1-917 Me Me H Pr-c SCH₂ Ph(2,6-F₂) 1-918 Me Me H Pr-c SOCH₂ Ph(2,6-F₂) 1-919 Me Me H Pr-c SO₂CH₂ Ph(2,6-F₂) 1-920 Me Me H H SO₂CH₂ CH₂OCH₂C≡CH

TABLE 38 Melting point (° C.) Compound or refractive No. R₁ R₂ R₃ R₄ Q Y index (n_(D) ²⁰) 1-921 Me Me H H SO₂CH₂ Ph(2-OC₂H₄CO₂Me) 1-922 Me Me H H SO₂CH₂ Ph(2-OC₂H₄COMe) 1-923 Me Me H H SO₂CH₂ Ph(2-CO₂Ph) 1-924 Me Me H H SCH₂ Ph(2,3,5-(Me)₃, 6-F) 1-925 Me Me H H SCH₂ Ph(2,3,5-(Me)₃, 6-Cl) 1-926 Me Me H H SCH₂ Ph(2,3,5-(Me)₃, 6-Br) 1-927 Me Et H H SCH₂ Ph(2,3,5-(Me)₃, 6-F) 1-928 Me Et H H SCH₂ Ph(2,3,5-(Me)₃, 6-Cl) 1-929 Me Et H H SCH₂ Ph(2,3,5-(Me)₃, 6-Br) 1-930 Me Me H H SOCH₂ Ph(2,3,5-(Me)₃, 6-F) 1-931 Me Me H H SOCH₂ Ph(2,3,5-(Me)₃, 6-Cl) 1-932 Me Me H H SOCH₂ Ph(2,3,5-(Me)₃, 6-Br) 1-933 Me Et H H SOCH₂ Ph(2,3,5-(Me)₃, 6-F) 1-934 Me Et H H SOCH₂ Ph(2,3,5-(Me)₃, 6-Cl) 1-935 Me Et H H SOCH₂ Ph(2,3,5-(Me)₃, 6-Br) 1-936 Me Me H H SO₂CH₂ Ph(2,3,5-(Me)₃, 6-F) 1-937 Me Me H H SO₂CH₂ Ph(2,3,5-(Me)₃, 6-Cl) 1-938 Me Me H H SO₂CH₂ Ph(2,3,5-(Me)₃, 6-Br) 1-939 Me Et H H SO₂CH₂ Ph(2,3,5-(Me)₃, 6-F) 1-940 Me Et H H SO₂CH₂ Ph(2,3,5-(Me)₃, 6-Cl) 1-941 Me Et H H SO₂CH₂ Ph(2,3,5-(Me)₃, 6-Br)

TABLE 39

Melting point (° C.) or Compound refractive index No. R₁ R₂ R₃ R₄ Q—Y (n_(D) ²⁰) 2-1  Me Me H H SO₂Me 82-84 2-2  Me Me H H SO₂Et 59-60 2-3  Me Me H H SO₂Pr 2-4  Me Me H H SO₂Pr-i 2-5  Me Me H H SO₂Bu 2-6  Me Me H H SO₂Bu-i 2-7  Me Me H H SO₂Bu-s 2-8  Me Me H H SO₂Bu-t 2-9  Me Me H H SO₂Hex 2-10 Me Me H H SO₂C₈H₁₇ 2-11 Me Me H H SO₂C₁₀H₂₁ 2-12 Me Et H H SO₂Me 1.4771 2-13 Me Et H H SO₂Et 1.4759 2-14 Me Et H H SO₂Pr 1.4742 2-15 Me Et H H SO₂Pr-i 1.4752 2-16 Me Et H H SO₂Bu 1.4711 2-17 Me Et H H SO₂Bu-i 1.4696 2-18 Me Et H H SO₂Bu-s 1.4750 2-19 Me Et H H SO₂Bu-t   30-31.5 2-20 Me Et H H SO₂Hex 2-21 Me Et H H SO₂C₈H₁₇ 1.4685 2-22 Me Et H H SO₂C₁₀H₂₁ 1.4705 2-23 Me Pr-c H H SO₂CH₂ 1.4921 2-24 Me H Me H SO₂Me 1.4778 2-25 Me —(CH₂)₄— H SO₂Me 1.5016 2-26 H —(CH₂)₅— H SO₂Me 1.5122 2-27 H —(CH₂)₆— H SO₂Me 1.5135 2-28 —(CH₂)₂— H H SO₂Me 65-67 2-29 —(CH₂)₃ H H SO₂Me 72-73

The present compound represented by the general formula [I] can be produced according to the processes shown below. However, the production process is not restricted to these. <Production Process 1>Steps 1 to 4

[wherein L is a leaving group such as halogen atom, phenylsulfonyl group which may be substituted with C₁ to C₄ alkyl group (e.g. p-toluenesulfonyl group), C₁ to C₄ alkylsulfonyl group (e.g. methylsulfonyl group) or the like (chlorine atom is preferred); and R₁, R₂, R₃, R₄, R₅, R₆, Y and m have the same definitions as given above].

The above production process is explained in detail on each step.

(Step 1)

A compound represented by the general formula [II] is reacted with a mercaptan derivative represented by the general formula [III] in the presence of a base in an appropriate solvent or without using any solvent (preferably in an appropriate solvent), or with a salt (which is a sodium salt or a potassium salt) of a mercaptan derivative represented by the general formula [III] in an appropriate solvent, whereby an intended sulfide derivative represented by the general formula [IV] can be obtained.

The solvent can be exemplified by ethers such as diethyl ether, diethoxyethane, dioxane, tetrahydrofuran (THF) and the like; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, dichlorobenzene and the like; amides such as N,N-dimethylacetamide, N,N-dimethylformamide (DMF), N-methyl-2-pyrrolidinone and the like; sulfur compounds such as dimethyl sulfoxide (DMSO), sulfolane and the like; aromatic hydrocarbons such as benzene, toluene, xylene and the like; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, tert-butanol and the like; ketones such as acetone, 2-butanone and the like; nitriles such as acetonitrile and the like; water; and mixtures thereof.

The base can be exemplified by metal hydrides such as sodium hydride and the like; alkali metal amides such as sodium amide, lithium diisopropylamide and the like; organic bases such as pyridine, triethylamine, 1,8-diazabicyclo[5.4.0]-7-undecene and the like; inorganic bases such as alkali metal hydroxide (e.g. sodium hydroxide or potassium hydroxide), alkaline earth metal hydroxide (e.g. calcium hydroxide or magnesium hydroxide), alkali metal carbonate (e.g. sodium carbonate or potassium carbonate), alkali metal bicarbonate (e.g. sodium hydrogencarbonate or potassium hydrogencarbonate) and the like; and alcohol metal salts such as sodium methoxide, potassium tert-butoxide and the like.

The reaction temperature is any temperature between 0° C. and the reflux temperature of the reaction system, preferably a temperature between 10 and 100° C. The reaction time differs depending upon the compounds used but is 0.5 to 24 hours.

(Step 2)

In the oxidation reaction of the sulfide derivative represented by the general formula [IV], the sulfide derivative of the general formula [IV] is reacted with an oxidizing agent (for example, an organic peroxide such as m-chloroperbenzoic acid, performic acid or peracetic acid, or an inorganic peroxide such as hydrogen peroxide, potassium permanganate or sodium periodate) in an appropriate solvent, whereby an intended sulfoxide derivative represented by the general formula [V] can be obtained.

The solvent can be exemplified by halogenated hydrocarbons such as dichloromethane, chloroform, dichloroethane, carbon tetrachloride, chlorobenzene, dichlorobenzene and the like; ethers such as dioxane, tetrahydrofuran (THF), dimethoxyethane, diethyl ether and the like; amides such as N,N-dimethylacetamide, N,N-dimethylformamide (DMF), N-methyl-2-pyrrolidinone and the like; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, tert-butanol and the like; ketones such as acetone, 2-butanone and the like; nitrites such as acetonitrile and the like; acetic acid; water; and mixtures thereof.

The reaction temperature is any temperature between 0° C. and the reflux temperature of the reaction system, preferably a temperature between 10 and 60° C. The reaction time differs depending upon the compounds used but is 1 to 72 hours.

(Step 3)

The sulfoxide derivative represented by the general formula [V] is reacted with an oxidizing agent (the same as described in the step 2) in an appropriate solvent (the same as described in the step 2), whereby an intended sulfone derivative represented by the general formula [VI] can be obtained.

The reaction temperature is any temperature between 0° C. and the reflux temperature of the reaction system, preferably a temperature between 10 and 60° C. The reaction time differs depending upon the compounds used but is 1 to 72 hours.

(Step 4)

When, in the oxidation reaction of the sulfide derivative represented by the general formula [IV], the oxidizing agent is used by an appropriate amount, the sulfone derivative represented by the general formula [VI] can be obtained without isolating the sulfoxide derivative represented by the general formula [V].

That is, the sulfide derivative represented by the general formula [IV] is reacted with an oxidizing agent (the same as described in the step 2) in an appropriate solvent (the same as described in the step 2), whereby an intended sulfoxide derivative represented by the general formula [V] can be obtained.

The reaction temperature is any temperature between 0° C. and the reflux temperature of the reaction system, preferably a temperature between 10 and 60° C. The reaction time differs depending upon the compounds used but is 1 to 72 hours.

A compound represented by the genera, formula [II] wherein L is a halogen atom, can be synthesized by the following step 5.

(Step 5)

[wherein X₁ is a halogen atom (a chlorine atom is preferred), and R₁, R₂, R₃ and R₄ have the same definitions as given above].

That is, a compound represented by the general formula [VIII] is reacted with an olefin derivative represented by the general formula [VII] in the presence of a base in an appropriate solvent or without using any solvent (preferably in an appropriate solvent), whereby isoxazoline compounds represented by the general formulas [IX] and [X] can be obtained. When both R₃ and R₄ are a hydrogen atom, an isoxazoline compound represented by the general formula [IX] is obtained preferentially.

The solvent can be exemplified by ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethyl ether, dioxane, tetrahydrofuran and the like; halogenated hydrocarbons such as dichloroethane, carbon tetrachloride, chlorobenzene, dichlorobenzene and the like; aromatic hydrocarbons such as benzene, toluene, xylene and the like; acetic acid esters such as ethyl acetate, butyl acetate and the like; water; and mixtures thereof.

The base can be exemplified by alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and the like; alkaline earth metal hydroxides such as calcium hydroxide, magnesium hydroxide and the like; alkali metal carbonates such as sodium carbonate, potassium carbonate and the like; alkali metal bicarbonates such as sodium hydrogencarbonate, potassium hydrogencarbonate and the like; alkali metal acetates such as sodium acetate, potassium acetate and the like; alkali metal fluorides such as sodium fluoride, potassium fluoride and the like; and organic bases such as pyridine, triethylamine, 1,8-diazabicyclo[5.4.0]-7-undecene and the like.

The reaction temperature is any temperature between 0° C. and the reflux temperature of the reaction system, preferably a temperature between 10 and 80° C. The reaction time differs depending upon the compounds used but is 0.5 hour to 2 weeks.

Incidentally, the compound represented by the general formula [VII] used in the above step 5 as an intermidiate can be a commercial product or synthesized by a known reaction such as Wittig reaction or the like. The compound represented by the general formula [VIII] can be synthesized by, for example, a method described in Liebigs Annalen der Chemie, p. 985 (1989).

<Production Process 2>Step 6

(wherein X₁, R₁, R₂, R₃, R₄, R₅, R₆, Y and m have the same definitions as given above; R₀ is a C₁ to C₄ alkyl group or a benzyl group, preferably a lower alkyl group such as methyl group, ethyl group or the like; and base is the same as described in the step 1).

The sulfide derivative represented by the general formula [IV], described in the Production Process 1 can be obtained also by the following process.

That is, a compound represented by the general formula [XI] is reacted with sodium hydrogensulfide hydrate represented by the general formula [XII] in the presence of a base (the same as described in the step 1) in an appropriate solvent or without using any solvent (preferably in an appropriate solvent) (Rongalit may be added in some cases), whereby a mercaptan salt represented by the general formula [XIII] can be obtained in the reaction system. The reaction mixture is reacted with a halogen derivative represented by the general formula [XIV] without isolating the mercaptan salt represented by the general formula [XIII], whereby a sulfide derivative represented by the general formula [IV] can be obtained.

The solvent can be exemplified by ethers such as dioxane, tetrahydrofuran (THF) and the like; halogenated hydrocarbons such as dichloromethane, carbon tetrachloride, chlorobenzene, dichlorobenzene and the like; amides such as N,N-dimethylacetamide, N,N-dimethylformamide (DMF), N-methyl-2-pyrrolidinone and the like; sulfur compounds such as dimethyl sulfoxide (DMSO), sulfolane and the like; aromatic hydrocarbons such as benzene, toluene, xylene and the like; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, tert-butanol and the like; ketones such as acetone, 2-butanone and the like; nitrites such as acetonitrile and the like; water; and mixtures thereof.

The reaction temperature is any temperature between 0° C. and the reflux temperature of the reaction system, preferably a temperature between 10 and 100° C. The reaction time differs depending upon the compounds used but is 0.5 to 24 hours.

The sulfone derivative represented by the general formula [XI] can be produced by the method shown in the Step 1 of the Production Process 1. In this case, the group —(CR₅R₆)_(n)—Y in the general formula [III] is an alkyl group or a benzyl group.

Next, the method for producing the present compound, the method for formulation with the present compound, and the application are specifically described by way of Examples. The method for producing the intermediate for the present compound is also described.

EXAMPLE 1 Production Of 3-benzylthio-5,5-dimethyl-2-isoxazoline (Present Compound No. 1-679)

To a solution of 2.8 g (22.5 mmoles) of benzylmercaptan dissolved in 50 ml of dimethylformamide were added, in a nitrogen current, 3.2 g (23.2 mmoles) of anhydrous potassium carbonate and 3.0 g (22.5 mmoles) of 3-chloro-5,5-dimethyl-2-isoxazoline. The mixture was stirred at 100° C. for 2 hours to give rise to a reaction. After the completion of the reaction, the reaction mixture was poured into water, followed by extraction with ethyl acetate. The resulting organic layer was washed with water and an aqueous sodium chloride solution in this order and then dried over anhydrous magnesium sulfate. The resulting solution was subjected to vacuum distillation to remove the solvent contained therein, and the residue was purified by silica gel column chromatography to obtain 3.1 g (yield: 62.0%) of 3-benzylthio-5,5-dimethyl-2-isoxazoline as a yellow oily substance (refractive index n_(D) ²⁰=1.5521).

¹H-NMR [CDCl₃/TMSδ(ppm)]: 7.24-7.39 (5H,m), 4.26 (2H,s), 2.77 (2H,s), 1.40 (6H,s)

<Example 2> Production Of 5-ethyl-3-(2,6-difluorobenzylsulfinyl)-5-methyl-2-isoxazoline (Present Compound No. 1-199)

To a solution of 4.1 g (15.0 mmoles) of 5-ethyl-3-(2,6-difluorobenzylthio)-5-methyl-2-isoxazoline dissolved in 50 ml of chloroform was added, with ice-cooling, 4.6 g (18.8 mmoles) of m-chloroperbenzoic acid (70%). The mixture was stirred for 1 hour and then at room temperature for 12 hours to give rise to a reaction. After the completion of the reaction, the reaction mixture was poured into water, followed by extraction with chloroform. The resulting organic phase was washed with an aqueous sodium hydrogensulfite solution, an aqueous potassium carbonate solution, water and an aqueous sodium chloride solution in this order, and then dried over anhydrous magnesium sulfate. The resulting solution was subjected to vacuum distillation to remove the solvent contained therein. The residue was purified by silica gel column chromatography (solvent system: hexane-ethyl acetate) to obtain 1.5 g (yield: 34.8%) of 5-ethyl-3-(2,6-difluorobenzylsulfinyl)-5-methyl-2-isoxazloline as a white powder (melting point: 30° C. or less).

¹H-NMR [CDCl₃/TMSδ(ppm)]: 7.39-7.28 (1H, m), 7.03-6.94 (2H, m), 4.38 (2H, s), 3.04 (1H, ABq, J=17.2, Δυ=85.7 Hz)+3.12 (1H, s) 1.75 (2H, m), 1.44 (3H, s)+1.41 (3H, 3), 0.97 (3H, m)

<Example 3> Production Of 5-ethyl-3- (2,6-difluorobenzylsulfonyl)-5-methyl-2-isoxazoline (Present Compound No. 1-200)

To a solution of 0.8 g (2.8 mmoles) of 5-ethyl-3-(2,6-difluorobenzylsulfinyl)-5-methyl-2-isoxazoline dissolved in 50 ml of chloroform was added, with ice-cooling, 1.0 g (4.1 mmoles) of m-chloroperbenzoic acid. The mixture was stirred for 1 hour and then at room temperature for 12 hours to give rise to a reaction. After the completion of the reaction, the reaction mixture was poured into water, followed by extraction with chloroform. The resulting organic phase was washed with an aqueous sodium hydrogensulfite solution, an aqueous potassium carbonate solution, water and an aqueous sodium chloride solution in this order, and then dried over anhydrous magnesium sulfate. The resulting solution was subjected to vacuum distillation to remove the solvent contained therein. The residue was purified by silica gel column chromatography (solvent system: hexane-ethyl acetate) to obtain 0.6 g (yield: 75.0%) of 5-ethyl-3-(2,6-difluorobenzylsulfonyl)-5-methyl-2-isoxazloline as a white powder (melting point: 64 to 65° C.).

¹H-NMR [CDCl₃/TMSδ(ppm)] 7.36-7.46 (1H,m), 6.98-7.04 (2H,m), 4.73 (2H,s), 3.04 (2H, ABq, J=17.2, Δυ-51.1 Hz), 1.77 (2H,q), 1.46 (3H,s), 0.97 (3H,t)

<Example 4> Production Of 3-(2,6-difluorobenzylsulfonyl)-5,5-dimethyl-2-isoxazoline (Present Compound No. 1-39)

To a solution of 3.9 g (15.2 mmoles) of 3-(2,6-difluorobenzylthio)-5,5-dimethyl-2-isoxazoline dissolved in 50 ml of chloroform was added, with ice-cooling, 8.5 g (34.5 mmoles) of m-chloroperbenzoic acid. The mixture was stirred for 1 hour and then at room temperature for 12 hours to give rise to a reaction. After the completion of the reaction, the reaction mixture was poured into water, followed by extraction with chloroform. The resulting organic phase was washed with an aqueous sodium hydrogensulfite solution, an aqueous potassium carbonate solution, water and an aqueous sodium chloride solution in this order, and then dried over anhydrous magnesium sulfate. The resulting solution was subjected to vacuum distillation to remove the solvent contained therein. The residue was washed with diisopropyl ether to obtain 3.4 g (yield: 77.3%) of 3-(2,6-difluorobenzylsulfonyl)-5,5-dimethyl-2-isoxazbline as a white powder (melting point: 110 to 111° C.).

¹H-NMR [CDCl₃/TMSδ(ppm)]: 7.35-7.45 (1H,m), 6.98-7.03 (2H,m), 4.72 (2H,s), 3.06 (2H,s), 1.51 (6H,s)

<Example 5> Production Of 3-(2,6-difluorobenzylthio)-5,5-dimethyl-2-isoxazoline (Present Compound No. 1-38)

To a solution of 5.0 g (28.2 mmoles) of 3-methylsulfonyl-5,5-dimethyl-2-isoxazoline (present compound No. 2-1) dissolved in 50 ml of DMF were added, with ice-cooling, 4.5 g (purity: 70%, 56.1 mmoles) of sodium hydrogensulfide hydrate, 7.8 g (56.4 mmoles) of potassium carbonate and 8.7 g (56.5 mmoles) of Rongalit. The mixture was stirred for 2 hours. Thereto was added 5.8 g (28.0 mmoles) of 2,6-difluorobenzylbenzyl bromide. The mixture was stirred at room temperature for 12 hours to give rise to a reaction. After the completion of the reaction, the reaction mixture was poured into water, followed by extraction with ethyl acetate. The resulting organic phase was washed with an aqueous sodium chloride solution and then dried over anhydrous magnesium sulfate. The resulting solution was subjected to vacuum distillation to remove the solvent contained therein. The residue was purified by silica gel column chromatography (solvent system=hexane-ethyl acetate) to obtain 5.8 g (yield: 80.0%) of 3-(2,6-difluorobenzylthio)-5,5-dimethyl-2-isoxazoline as a white powder (melting point: 77 to 80° C.).

¹H-NMR [CDCl₃/TMSδ(ppm)]: 7.20-7.28 (1H,m), 6.86-6.93 (2H,m), 4.35 (2H,s), 2.81 (2H,s), 1.43 (6H,s)<

<Example 6> Production Of 3-methylsulfonyl-5,5-dimethyl-2-isoxazoline (Present Compound No. 2-1)

To a solution of 193.0 g (1.07 M) of 3-chloro-5,5-dimethyl-2-isoxazoline dissolved in 500 ml of DMF was dropwise added, with ice-cooling, 1.0 kg (content=15%, 2.14 M) of an aqueous sodium methanethiolate solution. The mixture was stirred at room temperature for 12 hours to give rise to a reaction. After the completion of the reaction, the reaction mixture was poured into water, followed by extraction with ethyl acetate. The resulting organic phase was washed with an aqueous sodium chloride solution and then dried over anhydrous magnesium sulfate. The resulting solution was subjected to vacuum distillation to remove the solvent contained therein, to obtain 115.0 g (yield: 74.1%) of 3-methylthio-5,5-dimethyl-2-isoxazoline. This residue (141.2 mmoles) was dissolved in 1 liter of chloroform. Thereto was added, with ice-cooling, 392.0 g (1.59 M) of m-chloroperbenzoic acid (purity: 70%), followed by stirring at that temperature for 1 hour and at room temperature for 12 hours to give rise to a reaction. After the completion of the reaction, the precipitated m-chloroperbenzoic acid was removed by filtration. The filtrate was washed with an aqueous sodium hydrogensulfite solution, water, an aqueous sodium hydrogencarbonate solution and an aqueous sodium chloride solution in this order, and then dried over anhydrous magnesium sulfate. The resulting solution was subjected to vacuum distillation to remove the solvent contained therein. The residue was washed with diisopropyl ether to obtain 77.6 g (yield: 59.1%) of 3-methylsulfonyl-5,5-dimethyl-2-isoxazoline as a white powder (melting point: 82 to 84° C.).

¹H-NMR [CDCl₃/TMSδ(ppm)]: 3.26 (3H,s), 3.12 (2H,s), 1.51 (6H,s)

(Examples Of Production Of Intermediates) <Reference Example 1> Production Of 3-chloro-5,5-dimethyl-2-isoxazoline (Compound IX)

534.0 g (4.0 moles) of N-chlorosuccinimide was slowly added, at 65 to 70° C., to a solution of 182.7 g (2.05 moles) of glyoxylic aldoxime dissolved in 2 liters of dimethoxyethane, followed by refluxing for 1 hour with heating. Thereto were added, with ice-cooling, 1,440.0 g (14.4 moles) of potassium hydrogencarbonate and 10 ml of water. To the mixture was added 360.0 g (6.4 moles) of 2-methylpropene, followed by stirring at room temperature for 24 hours to give rise to a reaction. The reaction mixture was poured into water, followed by extraction with isopropyl ether. The resulting organic phase was washed with water and an aqueous sodium chloride solution in this order and then dried over anhydrous magnesium sulfate. The resulting solution was subjected to vacuum distillation to remove the solvent contained therein, to obtain 107.7 g (yield: 40.0%) of 3-chloro-5,5-dimethyl-2-isoxazoline as a yellow viscous liquid.

¹H-NMR [CDCl₃/TMSδ(ppm)]: 2.93 (2H,s), 1.47 (6H,s)

<Reference Example 2> Production Of 3-chloro-5-ethyl-5-methyl-2-isoxazoline (Compound IX)

61.9 g (463.4 mmoles) of N-chlorosuccinimide was slowly added, at 60° C., to a solution of 20.6 g (231.7 mmoles) of glyoxylic acid aldoxime dissolved in 500 ml of dimethoxyethane. Then, the mixture was refluxed for 10 minutes with heating. Thereto were added, with ice-cooling, 50 ml (463.4 mmoles) of 2-methyl-1-butene, 98.9 g (1,622 mmoles) of potassium hydrogencarbonate and 10 ml of water, followed by stirring for 12 hours to give rise to a reaction. The reaction mixture was poured into water, followed by extraction with n-hexane. The resulting organic layer was washed with water and an aqueous sodium chloride solution in this order and then dried over anhydrous magnesium sulfate. The resulting solution was subjected to vacuum distillation to remove the solvent contained therein, to obtain 13.9 g (yield: 40.6%) of 3-chloro-5-ethyl-5-methyl-2-isoxazoline as a light yellow viscous liquid.

¹H-NMR [CDCl₃/TMSδ(ppm)]: 2.91 (2H, Abq, J=17.0, Δυ=46.1 Hz), 1.73 (2H,q), 1.42 (3H,s), 0.96 (3H,t)

Below are shown the properties (¹H-NMR [CDCl₃/TMSδ(ppm)]) of the present compounds produced according to the Production Process 1 or the Production Process 2.

Present compound 1-602: 6.71-7.23 (3H,m), 4.84 (2H,s), 4.04 (2H,q), 2.81 (2H,s), 2.47 (3H,s), 1.42 (6H,s)

Present compound 1-603: 6.72-7.23 (3H,m), 4.85 (2H,s), 3.93 (2H,t), 2.82 (2H,s), 2.47 (3H,s), 1.83 (2H,m), 1.42 (6H,s), 1.04 (3H,t)

Present compound 1-605: 6.72-7.29 (3H,m), 4.85 (2H,s), 3.98 (2H,t), 2.81 (2H,s), 2.47 (3H,s), 1.80 (2H,m), 1.38 (6H,s), 0.97 (3H,t)

Present compound 1-606: 6.72-7.27 (3H,m), 6.05 (1H,m), 5.43 (1H,d), 5.29 (1H,d), 4.87 (2H,s), 4.57 (2H,d), 2.88 (2H,s), 2.48 (3H,s), 1.44 (6H,s)

Present compound 1-607: 6.92-7.30 (3H,m), 4.84 (2H,s), 4.71 (2H,d), 2.96 (2H,s) 2.52 (1H,s), 2.48 (3H,s), 1.46 (6H,s)

Present compound 1-228: 7.44-7.34 (2H,min), 7.02-6.92 (2H,m), 4.71 (2H,s), 3.86 (3H,s), 2.81 (2H, ABq, J=117.4, Δυ=54.2 Hz), 1.68 (2H,q), 1.36 (3H,s), 0.90 (3H,t)

Present cornpound 1-590: 7.28 (1H,dd), 7.08 (1H,d), 6.86 (1H,d), 6.05 (1H,m), 5.45 (1H,d), 5.32 (1H,d), 4.90 (2H,s), 4.63 (2H,d), 3.00 (2H,s), 1.47 (6H,s)

Present compound 1-599: 8.07 (1H,d), 7.47-7.56 (3H,m), 6.05 (1H,m), 5.42 (1H,d), 5.31 (1H,d), 5.31 (2H,s), 4.83 (2H,d), 2.94 (2H,s) 1.43 (6H,s)

The herbicide of the present invention contains, as the active ingredient, an isoxazoline derivative represented by the genera formula [I] or a salt thereof.

In using the compound of the present invention as a herbicide, the present compound may be used by itself. It can also be used in the form of a powder, a wettable powder, an emulsifiable concentrate, fine granules, granules, etc. by blending with a carrier, a surfactant, a dispersant, an adjuvant, etc. all generally used in formulation.

As the carrier used in formulation, there can be mentioned, for example, solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, calcium carbonate, slaked lime, siliceous sand, ammonium sulfate, urea and the like; and liquid carriers such as isopropyl alcohol, xylene, cyclohexane, methylnaphthalene and the like.

As the surfactant and the dispersant, there can be mentioned, for example, metal salts of alkylbenzenesulfonic acids, metal salts of dinaphthylmethanedisulfonic acid, salts of alcohol sulfates, alkylarylsulfonic acid salts, ligninsulfonic acid salts, polyoxyethylene glycol ether, polyoxyethylene alkyl aryl ethers, monoalkylates of polyoxyethylene sorbitan and the like. As the adjuvant, there can be mentioned, for example, carboxymethyl cellulose, polyethylene glycol and gum arabic. The present herbicide, when used, is diluted to an appropriate concentration and sprayed or applied directly.

The herbicide of the present invention can be used by spraying on plant foliage, application to soil, application on water surface, etc. The amount of the active ingredient used is determined appropriately so as to meet the application purpose. When the present compound is made into a powder or granules, the amount is appropriately determined in a range of 0.01 to 10% by weight, preferably 0.05 to 5% by weight. When the present compound is made into an emulsifiable concentrate or a wettable powder, the amount is appropriately determined in a range of 1 to 90% by weight, 5 to 50% by weight.

The amount of the present herbicide used varies depending upon the kind of the compound used, the target weed, the tendency of weed emergence, the environmental conditions, the type of the herbicide used, etc. When the present herbicide is used per se as in the case of a powder or granules, the amount is appropriately selected in a range of 0.1 g to 5 kg, preferably 1 g to 1 kg per 10 ares in terms of the active ingredient. When the present herbicide is used in a liquid form as in the case of an emulsifiable concentrate or a wettable powder, the amount is appropriately selected in a range of 0.1 to 50,000 ppm, preferably 10 to 10,000 ppm in terms of the active ingredient.

The compound of the present invention may be mixed as necessary with an insecticide, a fungicide, other herbicide, a plant growth-regulating agent, a fertilizer, etc.

Next, formulation from the present compound is described specifically by showing typical examples of formulation. The kinds of compounds and additives and their compounding ratios are not restricted to those shown below and can be varied widely. In the following description, “parts” refer to parts by weight.

<Formulation 1>Wettable Powder

10 parts of a compound (1-5) are mixed with 0.5 part of polyoxyethylene octylphenyl ether, 0.5 part of a sodium salt of a β-naphthalenesulfonic acid-formalin condensate, 20 parts of diatomaceous earth and 69 parts of clay. The mixture is mixed and pulverlized to obtain a wettable powder.

<Formulation 2>Wettable Powder

10 parts of a compound (1-5) are mixed with 0.5 part of polyoxyethylene octylphenyl ether, 0.5 part of a sodium salt of a β-naphthalenesulfonic acid-formalin condensate, 20 parts of diatomaceous earth, 5 parts of white carbon and 64 parts of clay. The mixture is mixed and pulverlized to obtain a wettable powder.

<Formulation 3>Wettable Powder

10 parts of a compound (1-5) are mixed with 0.5 part of polyoxyethylene octylphenyl ether, 0.5 part of a sodium salt of a β-naphthalenesulfonic acid-formalin condensate, 20 parts of diatomaceous earth, 5 parts of white carbon and 64 parts of calcium carbonate. The mixture is mixed and pulverlized to obtain a wettable powder.

<Formulation 4>Emulsifiable Concentrate

To 30 parts of a compound (1-5) are added 60 parts of an equal volume mixture of xylene and isophorone and 10 parts of a surfactant mixture of a polyoxyethylene sorbitan alkylate, a polyoxyethylene alkylaryl polymer and an alkylarylsulfonate. The resulting mixture is stirred sufficiently to obtain an emulsifiable concentrate.

<Formulation 5>Granules

There are mixed 10 parts of a compound (1-5), 80 parts of an extender which is a 1:3 mixture of talc and bentonite, 5 parts of white carbon, 5 parts of a surfactant mixture of a polyoxyethylene sorbitan alkylate, a polyoxyethylene alkylaryl polymer and an alkylarylsulfonate. The resulting mixture is kneaded sufficiently to form a paste. The paste is extruded through the eyes (diameter: 0.7 mm) of a sieve. The extrudate is dried and cut into a length of 0.5 to 1 mm to obtain granules.

Next, Test Examples of the present compound are described to show the effect of the present compound.

<Test Example 1> Test For Herbicidal Effect By Paddy Field Soil Treatment

A paddy field soil was filled in a plastic pot of 100 cm² and subjected to puddling. Then, seeds of Echinochloa oryzicola Vasing. (Eo) were sowed and water was filled in a depth of 3 cm. Next day, wettable powders produced in accordance with the Formulation 1 were diluted with water and dropped on the water surface. The application amount of each wettable powder was 100 g per 10 ares in terms of the active ingredient. Then, breeding was made in a greenhouse, and the herbicidal effect of each wettable powder was examined at the 21st day from the treatment in accordance with the standard shown in Table 40. The results are shown in Tables 41 to 43.

TABLE 40 Herbicidal effect (extent of growth inhibition) or Index phytotoxicity 5 A herbicidal effect or phytotoxicity of 90% or more 4 A herbicidal effect or phytotoxicity of 70% to less than 90% 3 A herbicidal effect or phytotoxicity of 50% to less than 70% 2 A herbicidal effect or phytotoxicity of 30% to less than 50% 1 A herbicidal effect or phytotoxicity of 10% to less than 30% 0 A herbicidal effect or phytotoxicity of 0% to less than 10%

TABLE 41 Application amount (active Herbicidal Compound ingredient), effect to No. g/10 a Eo 1-1 100 5 1-2 100 5 1-3 100 5 1-4 100 5 1-5 100 5 1-6 100 5 1-7 100 5 1-8 100 5 1-32 100 5 1-33 100 5 1-34 100 5 1-35 100 5 1-38 100 5 1-39 100 5 1-40 100 5 1-41 100 5 1-42 100 5 1-43 100 5 1-46 100 5 1-49 100 5 1-55 100 5 1-56 100 5 1-58 100 5 1-59 100 5 1-106 100 5 1-139 100 5 1-142 100 5 1-145 100 5 1-157 100 5 1-158 100 5 1-160 100 5 1-184 100 5 1-185 100 5 1-186 100 5 1-187 100 5 1-188 100 5 1-189 100 5 1-190 100 5 1-191 100 5 1-192 100 5 1-193 100 5 1-194 100 5 1-195 100 5 1-198 100 5 1-199 100 5 1-200 100 5 1-201 100 5 1-202 100 5 1-203 100 5 1-228 100 5 1-229 100 5 1-230 100 5 1-328 100 5 1-329 100 5 1-331 100 5 1-336 100 5 1-363 100 5 1-364 100 5 1-365 100 5 1-366 100 5 1-367 100 5 1-368 100 5 1-377 100 5 1-378 100 5 1-380 100 5 1-381 100 5 1-382 100 5 1-383 100 5 1-384 100 5 1-386 100 4 1-387 100 5 1-388 100 5 1-394 100 5 1-396 100 5 1-397 100 5 1-401 100 5 1-419 100 5 1-456 100 5 1-457 100 5

TABLE 42 Application amount (active Herbicidal Compound ingredient), effect to No. g/10 a Eo 1-487 100 5 1-488 100 5 1-489 100 5 1-490 100 5 1-491 100 5 1-492 100 5 1-493 100 5 1-494 100 5 1-495 100 5 1-496 100 5 1-497 100 5 1-498 100 5 1-499 100 5 1-500 100 5 1-501 100 5 1-502 100 5 1-503 100 5 1-504 100 5 1-505 100 5 1-506 100 5 1-507 100 5 1-508 100 5 1-509 100 5 1-510 100 5 1-511 100 5 1-512 100 5 1-513 100 5 1-514 100 5 1-515 100 5 1-516 100 5 1-517 100 5 1-518 100 5 1-519 100 5 1-520 100 5 1-521 100 5 1-522 100 5 1-523 100 5 1-524 100 5 1-525 100 5 1-526 100 5 1-527 100 5 1-528 100 5 1-529 100 5 1-530 100 5 1-531 100 5 1-532 100 5 1-533 100 5 1-534 100 5 1-535 100 5 1-536 100 5 1-537 100 5 1-538 100 5 1-539 100 5 1-540 100 5 1-541 100 5 1-542 100 5 1-543 100 5 1-544 100 5 1-545 100 5 1-546 100 5 1-547 100 5 1-548 100 5 1-549 100 5 1-550 100 5 1-551 100 5 1-552 100 4 1-553 100 5 1-554 100 5 1-555 100 5 1-556 100 5 1-559 100 5 1-560 100 5 1-561 100 5 1-562 100 5 1-563 100 5 1-564 100 5 1-565 100 5 1-566 100 5 1-567 100 5 1-568 100 5

TABLE 43 Application amount (active Herbicidal Compound ingredient), effect to No. g/10 a Eo 1-569 100 5 1-570 100 5 1-571 100 5 1-572 100 5 1-573 100 5 1-574 100 5 1-575 100 5 1-576 100 5 1-579 100 5 1-580 100 5 1-581 100 5 1-583 100 5 1-584 100 5 1-585 100 5 1-586 100 5 1-588 100 5 1-589 100 5 1-590 100 5 1-591 100 5 1-593 100 5 1-594 100 5 1-595 100 5 1-596 100 5 1-597 100 5 1-598 100 5 1-599 100 5 1-600 100 5 1-601 100 5 1-602 100 5 1-603 100 5 1-604 100 5 1-605 100 5 1-606 100 5 1-607 100 5 1-608 100 5 1-609 100 5 1-610 100 5 1-612 100 5 1-613 100 5 1-614 100 5 1-615 100 5 1-616 100 5 1-617 100 5 1-618 100 5 1-619 100 5 1-620 100 5 1-621 100 5 1-622 100 5 1-623 100 5 1-624 100 5 1-625 100 5 1-626 100 5 1-627 100 5 1-628 100 5 2-2 100 5 2-28 100 5 2-29 100 5

<Test Example 2> Test For Herbicidal Effect By Upland Field Soil Treatment

An upland field soil was filed in a plastic pot of 80 cm². Seeds of Echinochloa crus-galli (L.) Beauv. var. crusgall (Ec) and Setaria viridis (L.) Beauv. (Se) were sowed, followed by covering with the same soil. Wettable powders produced in accordance with the Formulation 1 were diluted with water and sprayed uniformly: on the soil surface using a small sprayer, in an amount of 100 liters per 10 ares so that the amount of each active ingredient became 100 g per 10 ares. Then, breeding was made in a greenhouse, and the herbicidal effect of each wettable powder was examined at the 21st day from the treatment in accordance with the standard shown in Table 40. The results are shown in Tables 44 to 46.

TABLE 44 Application amount (active Herbicidal Compound ingredient), effect to No. g/10 a Ec Se 1-1 100 5 5 1-2 100 5 5 1-3 100 5 5 1-4 100 5 5 1-5 100 5 5 1-6 100 5 5 1-7 100 5 5 1-8 100 5 5 1-32 100 5 5 1-33 100 5 5 1-34 100 5 5 1-35 100 5 5 1-38 100 4 4 1-39 100 5 5 1-40 100 5 5 1-41 100 5 5 1-42 100 5 4 1-43 100 5 5 1-46 100 5 5 1-49 100 5 5 1-55 100 5 5 1-56 100 5 5 1-58 100 5 5 1-59 100 5 5 1-106 100 5 5 1-139 100 5 5 1-142 100 5 5 1-145 100 5 5 1-157 100 5 5 1-158 100 5 5 1-160 100 5 5 1-184 100 5 4 1-185 100 5 5 1-186 100 5 5 1-187 100 5 5 1-188 100 5 5 1-189 100 5 5 1-190 100 5 5 1-191 100 5 5 1-192 100 5 5 1-193 100 5 4 1-194 100 5 5 1-195 100 5 5 1-198 100 4 5 1-199 100 5 5 1-200 100 5 5 1-201 100 5 5 1-202 100 5 4 1-203 100 5 4 1-228 100 5 5 1-229 100 5 5 1-328 100 4 4 1-329 100 5 5 1-331 100 5 5 1-336 100 5 5 1-363 100 5 4 1-364 100 5 5 1-366 100 5 5 1-368 100 5 4 1-378 100 5 5 1-380 100 5 4 1-381 100 4 4 1-382 100 5 5 1-383 100 5 4 1-384 100 5 4 1-387 100 5 4 1-388 100 5 5 1-394 100 4 — 1-396 100 4 5 1-487 100 5 5 1-488 100 5 4 1-489 100 5 5 1-490 100 5 4 1-491 100 5 5 1-492 100 5 5 1-493 100 5 4 1-494 100 5 5 1-495 100 5 5 1-496 100 5 4 1-497 100 5 5

TABLE 45 Application amount (active Herbicidal Compound ingredient), effect to No. g/10 a Ec Se 1-498 100 5 5 1-499 100 5 5 1-500 100 5 5 1-501 100 5 5 1-502 100 5 5 1-503 100 5 5 1-504 100 5 5 1-505 100 5 5 1-506 100 5 5 1-507 100 5 5 1-508 100 5 5 1-509 100 5 5 1-510 100 5 5 1-511 100 5 5 1-512 100 5 5 1-513 100 5 5 1-514 100 5 5 1-515 100 5 5 1-516 100 5 5 1-517 100 5 5 1-518 100 5 4 1-520 100 5 5 1-521 100 5 5 1-522 100 5 5 1-523 100 5 5 1-524 100 5 5 1-525 100 5 5 1-526 100 5 5 1-527 100 5 5 1-528 100 5 5 1-529 100 5 5 1-530 100 5 5 1-531 100 5 5 1-532 100 5 4 1-534 100 5 5 1-535 100 5 5 1-536 100 5 5 1-537 100 5 5 1-538 100 5 5 1-539 100 5 5 1-540 100 5 5 1-541 100 5 5 1-542 100 5 5 1-543 100 5 5 1-544 100 5 5 1-545 100 5 5 1-546 100 5 4 1-547 100 5 5 1-548 100 5 5 1-549 100 5 5 1-550 100 5 5 1-551 100 5 5 1-553 100 5 5 1-554 100 5 5 1-555 100 5 5 1-556 100 5 4 1-559 100 5 5 1-560 100 5 5 1-561 100 5 5 1-562 100 5 5 1-563 100 5 5 1-564 100 5 5 1-565 100 5 5 1-566 100 5 5 1-567 100 5 5 1-568 100 5 5 1-569 100 5 5 1-570 100 5 5 1-571 100 5 — 1-572 100 5 5 1-573 100 5 5 1-574 100 5 5 1-576 100 5 5 1-580 100 5 — 1-581 100 5 5 1-583 100 5 5 1-585 100 5 5 1-586 100 5 5 1-589 100 5 5 1-590 100 5 5

TABLE 46 Application amount (active Herbicidal Compound ingredient), effect to No. g/10 a Ec Se 1-591 100 5 5 1-593 100 5 4 1-594 100 5 4 1-595 100 5 5 1-596 100 5 5 1-597 100 5 4 1-599 100 5 5 1-600 100 5 — 1-601 100 5 — 1-602 100 5 5 1-603 100 5 5 1-604 100 5 5 1-605 100 5 4 1-606 100 5 5 1-607 100 5 5 1-608 100 5 5 1-609 100 5 5 1-610 100 5 5 1-615 100 5 5 1-616 100 5 — 1-617 100 5 5 1-618 100 5 5 1-619 100 5 4 1-620 100 5 5 1-621 100 5 4 1-622 100 5 — 2-29 100 5 5

<Test Example 3> Test For Herbicidal Effect By Upland Foliage Treatment

An upland field soil was filed in a plastic pot of 80 cm². Seeds of Echinochloa crus-galli (L.) Beauv. var. crusgalli (Ec) were sowed. Breeding was made in a greenhouse for 2 weeks. Wettable powders produced in accordance with the Formulation 1 were diluted with water and sprayed on the whole foliage of plants from above the plants using a small sprayer in an amount of 100 liters per 10 ares so that the amount of each active ingredient became 100 g per 10 ares. Then, breeding was made in the greenhouse, and the herbicidal effect of each wettable powder was examined at the 14th day from the treatment in accordance with the standard shown in Table 40. The results are shown in Tables 47 and 48.

TABLE 47 Application amount (active Herbicidal Compound ingredient), effect to No. g/10 a Ec 1-1 100 5 1-2 100 4 1-3 100 4 1-4 100 4 1-5 100 5 1-6 100 4 1-7 100 4 1-8 100 5 1-32 100 5 1-35 100 4 1-39 100 5 1-40 100 5 1-43 100 5 1-46 100 4 1-49 100 5 1-55 100 4 1-56 100 5 1-58 100 5 1-59 100 5 1-106 100 4 1-139 100 4 1-142 100 4 1-145 100 4 1-157 100 5 1-158 100 5 1-160 100 5 1-184 100 4 1-185 100 5 1-186 100 5 1-187 100 5 1-188 100 4 1-192 100 4 1-193 100 5 1-199 100 4 1-200 100 4 1-201 100 5 1-202 100 4 1-203 100 4 1-229 100 4 1-336 100 5 1-363 100 4 1-364 100 4 1-366 100 4 1-378 100 5 1-380 100 4 1-383 100 4 1-397 100 4 1-487 100 4 1-488 100 4 1-489 100 4 1-490 100 4 1-491 100 4 1-492 100 4 1-494 100 5 1-495 100 5 1-496 100 5 1-497 100 5 1-498 100 5 1-499 100 5 1-500 100 5 1-501 100 5 1-502 100 5 1-503 100 4 1-504 100 5 1-505 100 5 1-506 100 4 1-507 100 4 1-508 100 4 1-509 100 4 1-510 100 4 1-511 100 5 1-512 100 5 1-513 100 5 1-514 100 5 1-515 100 5 1-516 100 5 1-517 100 5 1-520 100 4 1-521 100 5 1-522 100 5

TABLE 48 Application amount (active Herbicidal Compound ingredient), effect to No. g/10 a Ec 1-523 100 5 1-524 100 5 1-525 100 5 1-526 100 5 1-527 100 5 1-528 100 5 1-529 100 5 1-530 100 5 1-531 100 5 1-532 100 4 1-534 100 5 1-535 100 4 1-536 100 4 1-537 100 4 1-538 100 5 1-539 100 5 1-540 100 5 1-541 100 4 1-542 100 4 1-543 100 4 1-544 100 5 1-545 100 5 1-547 100 5 1-548 100 5 1-550 100 5 1-553 100 5 1-554 100 5 1-555 100 4 1-556 100 4 1-559 100 5 1-560 100 4 1-561 100 4 1-562 100 4 1-563 100 4 1-564 100 4 1-565 100 4 1-566 100 4 1-567 100 4 1-568 100 5 1-569 100 5 1-570 100 5 1-571 100 5 1-572 100 4 1-573 100 5 1-574 100 4 1-576 100 5 1-581 100 4 1-583 100 4 1-584 100 5 1-585 100 5 1-586 100 5 1-589 100 4 1-590 100 4 1-591 100 4 1-593 100 4 1-595 100 4 1-599 100 4 1-602 100 4 1-603 100 4 1-604 100 5 1-606 100 4 1-607 100 5 1-608 100 5 1-609 100 5 1-616 100 5

<Test Example 4> Test For Crop Selectivity By Paddy Field Soil Treatment

A paddy field soil was filled in a plastic pot of 100 cm² and subjected to puddling. Seeds of Echinochloa oryzicola Vasing. (Eo) were sowed; two-leaf stage seedlings of rice (Or) were transplanted in a depth of 2 cm; and water was filled in a depth of 3 cm. Next day, wettable powders produced in accordance with the Formulation 1 were diluted with water and dropped on the water surface. The application amount of each wettable powder was 100 g per 10 ares in terms of the active ingredient. Then, breeding was made in a greenhouse. At the 21st day from the treatment, the phytotoxicity and herbicidal effect of each wettable powder were examined in accordance with the standard shown in Table 40. The results are shown in Table 49.

TABLE 49 Application amount of active Herbicidal Compound ingredient Phytotoxicity effect No. g/10 a to Or to Eo 1-145 100 0 5 1-190 100 1 5 1-198 100 1 5 1-203 100 1 5 1-228 100 1 5 1-229 100 1 5 1-230 100 0 5 1-328 100 0 5 1-331 100 0 5 1-365 100 1 5 1-367 100 1 5 1-368 100 1 5 1-377 100 0 5 1-384 100 0 5 1-386 100 0 4 1-394 100 1 5 1-401 100 0 5 1-419 100 1 5 1-456 100 0 5 1-457 100 1 5 1-503 100 0 5 1-518 100 1 5 1-519 100 0 5 1-520 100 1 5 1-549 100 1 5 1-552 100 1 4 1-556 100 0 5 1-574 100 1 5 1-579 100 1 5 1-580 100 1 5 1-584 100 1 5 1-588 100 1 5 1-590 100 1 5 1-594 100 1 5 1-596 100 1 5 1-597 100 1 5 1-598 100 1 5 1-599 100 1 5 1-601 100 1 5 1-605 100 1 5 1-610 100 1 5 1-612 100 0 5 1-613 100 0 5 1-614 100 0 5 1-615 100 1 5 1-620 100 1 5 1-622 100 1 5 1-623 100 1 5 1-624 100 1 5 1-625 100 1 5 1-626 100 0 5 1-627 100 1 5 1-628 100 0 5 2-2 100 0 5 2-29 100 1 5

<Test Example 5> Test For Herbicidal Effect During Breeding Period By Paddy Field Water Treatment

A paddy field soil was filled in a plastic pot of 100 cm² and subjected to puddling. Seeds of Monochoria vaginalis Presl (Mo) and Scirpus juncoides Roxb. subsp. juncoides Roxb. (Sc) were sowed; water was filled in a depth of 3 cm; and breeding was made. When Mo reached a 1-leaf stage and Sc reached a 2-leaf stage, wettable powders produced in accordance with the Formulation 1 were diluted with water and dropped on the water surface. The application amount of each wettable powder was 100 g per 10 ares in terms of the active ingredient. Then, breeding was made in a greenhouse. At the 30th day from the treatment, the herbicidal effect of each wettable powder was examined in accordance with the standard shown in Table 40. The results are shown in Table 51. Incidentally, the details of comparative compounds 1 and 2 are shown in Table 50.

TABLE 50 Patent No. and Com- Compound Structural formula pound No. Comparative compound 1

JP-A-8- 225548 and 2012 Comparative compound 2

JP-A-8- 225548 and 2059 Comparative compound 3

JP-A-8- 225548 and 2034

TABLE 51 Application amount Compound of active ingredient Herbicidal effect to No. g/10 a Mo Sc 1-8 25 5 4 1-39 25 5 5 1-49 25 5 5 1-58 25 4 5 1-157 25 5 5 1-382 25 5 4 1-547 25 5 5 1-567 25 5 5 Comparative 25 1 1 compound 1 Comparative 25 1 1 compound 2

<Test Example 6>

Test for herbicidal effect to broadleaf weeds by upland field soil treatment

An upland field soil was filled in a plastic pot of 80 cm². Seeds of Polygonum lapathifolium L. subsp. nodosum (Pers.) Kitam. (Po) and Chenopodium album L. (Ch) were sowed, followed by covering with the same soil. Wettable powders produced in accordance with the Formulation 1 were diluted with water and sprayed uniformly on the soil surface using a small sprayer, in an amount of 100 liters per 10 ares so that the amount of each active ingredient became 100 g per 10 ares. Then, breeding was made in a greenhouse. At the 30th day from the treatment, the herbicidal effect of each wettable powder was examined in accordance with the standard shown in Table 40. The results are shown in Table 52. Incidentally, the details of comparative compounds 1 and 3 are shown in Table 50.

TABLE 52 Application amount Compound of active ingredient Herbicidal effect to No. g/10 a Po Ch 1-2 25 — 4 1-39 25 4 5 1-46 25 5 4 1-498 25 5 5 1-499 25 5 4 1-500 25 5 4 1-501 25 5 5 1-523 25 5 5 1-526 25 5 5 1-532 25 5 5 1-534 25 5 5 1-555 25 5 4 1-573 25 5 5 Comparative 1 25 0 0 Comparative 3 25 1 0

Industrial Applicability

The compound represented by the general formula [I] according to the present invention shows an excellent herbicidal effect, at a low application amount over a wide period, from before germination to growth, to various weeds causing problems in upland fields, for example, Gramineae weeds [e.g. Echinochloa crus-galli (L.) Beauv. var. crus-galli, Digitaria ciliaris (Retz.) Koeler, Setaria viridis (L.) Beauv., Poa annua L., Sorghum halepense (L.) Pers., Alopecurus aequalis Sobol. var. amurensis (Komar.) Ohwi, and wild oats], broadleaf weeds [Polygonum lapathifolium L. nodosum (Pers.) Kitam., Amaranthus viridis L., Chenopodium album L., Stellaria media (L.) Villars, Abutilon avicennae, Sida spinosa, cassia obtusifolia, Ambrosia artemisiifolia L. var. elatior (L.) Desc., and morning glory], and perennial or annual cyperaceous weeds [e.g. Cyperus rotundus L., cyperus esculentus, Kyllinga brevifolia Rottb. subsp. leiolepis (Fraxch. et Savat.) T. Koyama, Cyperus microiria Steud., and Cyperus iria L.].

Further, the present compound shows a herbicidal effect, at a low application amount over a wide period from before germination to growth, also to weeds emerging in paddy fields, i.e. annual weeds [e.g. Echinochloa oryzicola Vasing., Cyperus difformis L., Monochoria vaginalis (Burm. f.) Presl. var. plantaginea (Roxb.) Solms-Laub., and Lindernia pyxidara L.] and perennial weeds [e.g. Cyperus serotinus Rottb., Eleocharis kuroguwai Ohwi, and Scirpus juncoides Roxb. subsp. hotarui (Ohwi) T. Koyama].

The herbicide of the present invention has high safety to crops, particularly to rice, wheat, barley, corn, grain sorghum, soybean, cotton, sugar beat, lawn, fruit trees, etc. 

1. An isoxazoline derivative represented by the following general formula [I] or a salt thereof:

wherein Q is a group represented by —S(O)_(n)—(CR₅R₆)_(m)- (wherein n is 0 or an integer of 1 to 2, m is an integer of 1 to 3, and R₅ and R₆ are each independently a hydrogen atom, a cyano group, an alkoxycarbonyl group or a C₁ to C⁶ alkyl group); R₁ and R₂ are each independently a hydrogen atom, a C₁ to C₈ alkyl group [which may be substituted with C₃ to C₈ cycloalkyl group, C₁ to C₆ alkoxy group, C₁ to C₆ alkylcarbonyl group, C₁ to C₆ alkylthio group, C₁ to C₆ alkylsulfinyl group, C₁ to C₆ alkylsulfonyl group, C₁ to C₆ alkylamino group, di(C₁ to C₆ alkyl)amino group, cyano group, C₁ to C₆ alkoxycarbonyl group, C₁ to C₆ alkylaminocarbonyl group, di(C₁ to C₆ alkyl)aminocarbonyl group, (C₁ to C₆ alkylthio)carbonyl group, carboxyl group, optionally substituted benzyloxy group, optionally substituted phenoxy group, or optionally substituted phenyl group], a C₃ to C₈ cycloalkyl group, a C₁ to C₆ alkoxycarbonyl group, a C₃ to C₈ alkylaminocarbonyl group, a di (C₁ to C₆ alkyl) aminocarbonyl group, a C₁ to C₆ alkylthiocarbonyl group, a carboxyl group or an optionally substituted phenyl group; R₃ and R₄ are each independently a hydrogen atom, a C₁ to C₈ alkyl group (which may be substituted with 1 to 3 same or different, C₃ to C₈ cycloalkyl groups or C₁ to C₆ alkoxy groups) or a C₃ to C₈ cycloalkyl group; and Y is a phenyl group substituted with 1 to 5 same or different R₇; each R₇ is a hydrogen atom, a C₁ to C₆ alkyl group [which may be substituted with 1 to 3 same or different halogen atoms, C₁ to C₆ alkoxy groups, hydroxyl groups, C₁ to C₆ alkylthio groups, C₁ to C₆ alkylsulfinyl groups, C₁ to C₆ alkylsulfonyl groups, C₁ to C₆ alkylamino groups, di(C₁ to C₆)alkylamino groups, cyano groups or optionally substituted phenoxy groups], a C₁ to C₆ alkoxy group (which may be substituted with 1 to 3 same or different halogen atoms, C₁ to C₆ alkoxy groups, C₂ to C₆ alkenyl groups, C₁ to C₆ alkynyl groups, C₁ to C₆ alkoxycarbonyl groups, C₁ to C₆ alkylcarbonyl groups or C₃ to C₈ cycloalkyl groups), a C₂ to C₆ alkenyl group, a C₃ to C₈ cycloalkyloxy group, a C₁ to C₆ alkylthio group (which may be substituted with 1 to 3 same or different halogen atoms or C₁ to C₆ alkoxy groups), a C₁ to C₆ alkylsulfinyl group (which may be substituted with 1 to 3 same or different halogen atoms or C₁ to C₆ alkoxy groups), a C₁ to C₆ alkylsulfonyl group (which may be substituted with 1 to 3 same or different halogen atoms or C₁ to C₆ alkoxy groups), an optionally substituted benzyloxy group, an amino group [which may be substituted with C₁ to C₆ alkyl group, C₁ to C₆ alkylsulfonyl group, C₁ to C₆ alkylcarbonyl(C₁ to C₆ alkyl) group or C₁ to C₆ alkylsulfonyl (C₁ to C₆ alkyl) group], a di(C₁ to C₆ alkyl)amino group, a halogen atom, a cyano group, a nitro group, a C₁ to C₆ alkoxycarbonyl group, a C₃ to C₈ cycloalkyloxycarbonyl group, a carboxyl group, a C₂ to C₆ alkenyloxycarbonyl group, a C₂ to C₆ alkynyloxycarbonyl group, an optionally substituted benzyloxycarbonyl group, an optionally substituted phenoxycarboriyl group or a C₁ to C₆ alkylcarbonyloxy group; provided that compounds wherein R₁₁ R₂, R₃ and R₄ are hydrogen at the same time are excluded.
 2. An isoxazoline derivative or a salt thereof according to claim 1, wherein in the general formula [I], Q is a group represented by —S(O)_(n)—(CR₅R₆)_(m)- (wherein n is 0 or an integer of 1 to 2, m is 1, and R₅ and R₆ are a hydrogen atom); R₁ and R₂ are each independently a hydrogen atom, a C₁ to C₈ alkyl group (which may be substituted with C₃ to C₈ cycloalkyl group or C₁ to C₆ alkoxy group) or a C₃ to C₈ cycloalkyl group; R₃ and R₄ are each independently a hydrogen atom or a C₁ to C₈ alkyl group (which may be substituted with 1 to 3 same or different, C₃ to C₈ cycloalkyl groups or C₁ to C₆ alkoxy groups); and Y is a phenyl group substituted with 1 to 5 same or different R₇; each R₇ is a hydrogen atom, a C₁ to C₆ alkyl group [which may be substituted with 1 to 3 same or different halogen atoms, C₁ to C₆ alkoxy groups, hydroxyl groups, C₁ to C₆ alkylthio groups, C₁ to C₆ alkylsulfinyl groups, C₁ to C₆ alkylsulfonyl groups, C₁ to C₆ alkylamino groups, C₁ to C₆ dialkylamino groups, cyano groups or optionally substituted phenoxy groups], a C₁ to C₆ alkoxy group (which may be substituted with 1 to 3 same or different halogen atoms, C₁ to C₆ alkoxy groups, C₂ to C₆ alkenyl groups, C₂ to C₆ alkynyl groups, C₁ to C₆ alkoxycarbonyl groups, C₁ to C₆ alkylcarbonyl groups or C₃ to C₈ cycloalkyl groups), a C₃ to C₈ cycloalkyloxy group or a halogen atom; provided that compounds wherein R₁, R₂, R₃ and R₄ are hydrogen at the same time are excluded.
 3. An isoxazoline derivative or a salt thereof according to claim 1, wherein in the general formula [I], Q is a group represented by —S(O)_(n)—(CR₅R₆)_(m)- (wherein n is 0 or an integer of 1 to 2, m is 1, and R₅ and R₆ are a hydrogen atom); R₁ and R₂ are a C₁ to C₈ alkyl group; R₃ and R₁ are a hydrogen atom; Y is a phenyl group substituted with 1 to 5 same or different R₇; each R₇ is a hydrogen atom, a C₁ to C₆ alkyl group (which may be substituted with 1 to 3 same or different halogen atoms or C₁ to C₆ alkoxy groups), a C₁ to C₆ alkoxy group (which may be substituted with 1 to 3 same or different halogen atoms or C₁ to C₆ alkoxy groups), or a halogen atom.
 4. A herbicidal formulation containing, as the active ingredient, an isoxazoline derivative or its salt set forth in claim
 1. 5. A herbicidal formulation containing, as the active ingredient, an isoxazoline derivative or its salt set forth in claim
 2. 6. A herbicidal formulation containing, as the active ingredient, an isoxazoline derivative or its salt set forth in claim
 3. 7. An isoxazoline compound or a salt according to claim 1, wherein m is 1; and R₁ and R₂ are each independently a hydrogen atom, a C₁ to C₈ alkyl group [which may be substituted with C₁ to C_(H) cycloalkyl group, C₁ to C₆ alkoxy group, C₁ to C₆ alkylcarbonyl group, C₁ to C₆ alkylthio group, C₁ to C₆ alkylsulfinyl group, C₁ to C₆ alkylsulfonyl group, C₁ to C₆ alkylamino group, di(C₁ to C₆ alkyl)amino group, cyano group, C₁ to C₆ alkoxycarbonyl group, C₁ to C₆ alkylaminocarbonyl group, di(C₁ to C₆ alkyl)aminocarbonyl group, (C₁ to C₆ alkylthio)carbonyl group, carboxyl group, optionally substituted benzyloxy group, optionally substituted phenoxy group, or optionally substituted phenyl group], a C₃ to C₈ cycloalkyl group, a C₁ to C₆ alkoxycarbonyl group, a C₁ to C₆ alkylaminocarbonyl group, a di(C₁ to C₆ alkyl)aminocarbonyl group, a (C₁ to C₆ alkylthio)carbonyl group, a carboxyl group or an, optionally substituted pheryl group.
 8. An isoxazoline compound or a salt according to claim 1, wherein m is 1; R₅ and R₆ are each independently a hydrogen atom or a C₁ to C₆ alkyl group; R₁ and R₂ are cash independently a hydrogen atom, a C₁ to C_(H) alkyl group [which may be substituted with C₃ to C₈ cycloalkyl group or C₁ to C₆ alkoxy group], or a C₃ to C₈ cycloalkyl group; and R₃ and R₄ are each independently a hydrogen atom or a C₁ to C₈ alkyl group [which may be substituted with 1 to 3 same or different, C₃ to C₈ cycloalkyl group or C₁ to C₆ alkoxy group].
 9. An isoxazoline compound or a salt according to claim 1, wherein m is 1; R₃ and R₆ are each independently a hydrogen atom or a C₁ to C₆ alkyl group; R₁ and R₂ are each independently a hydrogen atom, a C₁ to C₈ alkyl group which may be substituted with C₃ to C₈ cycloalkyl group, or a C₃ to C₈ oycloalkyl group; and R₃ and R₄ are each independently a hydrogen atom or a C₁ to C₈ alkyl group.
 10. An isoxazoline compound or a salt according to claim 1, wherein m is 1; R₅ and R₆ are each independently a hydrogen atom or a C₁ to C₆ alkyl group; R₁ and R₂ are each independently a hydrogen atom, a C₁ to C₈ alkyl group which may be substituted with C₃ to C₈ cycloalkyl group, or a C₃ to C₈ cycloalkyl group; R₃ and R₄ are each independently a hydrogen atom or a C₁ to C₈ alkyl group; and Y is a hydrogen atom, a C₁ to C₁₀ alkyl group which may be substituted with 1 to 3 same or different halogen atoms, or a phenyl group substituted with 1 to 5 same or different R₇; R₇ is a hydrogen atom, a C₁ to C₆ alkyl group which may be substituted with 1 to 3 same or different halogen atoms, a C₁ to C₆ alkoxy group [which may be substituted with 1 to 3 same or different halogen atoms, C₂ to C₆ alkenyl group, C₂ to C₆alkynyl group, or C₃ to C₆ cycloalkyl group], a C₃ to C₈ cycloalkyloxy group, a C₁ to C₆ alkylthio group [which may be substituted with 1 to 3 same or different halogen atoms or C₁ to C₆ alkoxy group], a halogen atom, a cyano group, a nitro group, a C₁ to C₆ alkoxycarbonyl group, or a C₃ to C₈ cycloalkyloxycarbonyl group.
 11. An isoxazoline compound or a salt according to claim 1, wherein Q is a group represented by —S(O)_(n)—(CR₅R₆)_(m)- (wherein n is 2, m is 1 and R₅ and R₆ are a hydrogen atom); R₁ and R₂ are each independently a C₁ to C₃ alkyl group; R₃ and R₄ are a hydrogen atom; and Y is a phenyl group substituted with 1 to 5 same or different R₇; R₇ is a hydrogen atom, a C₁ to C₆ alkyl group which may be substituted with 1 to 3 same or different halogen atoms or a C₁ to C₆ alkoxy group, a C₁ to C₆ alkoxy group which may be substituted with 1 to 3 same or different halogen atoms or a C₁ to C₆ alkoxy group, or a halogen atom.
 12. An isoxazoline compound or a salt according to claim 1, wherein Q is a group represented by —S(O)_(n)—(CR₅R₆)_(m)- (wherein n is 2, m is 1 and R₅ and R₆ are a hydrogen atom); R₁ and R₂ are a methyl group; R₃ and R₄ are a hydrogen atom; and Y is a phenyl group substituted with 1 to 5 same or different R₇; R₇ is a hydrogen atom, a C₁ to C₆ alkyl group which may be substituted with 1 to 3 same or different halogen atoms, a C₁ to C₆ alkoxy group which may be substituted with 1 to 3 same or different halogen atoms, or a halogen atom.
 13. An isoxazoline compound or a salt according to claim 1, wherein Q is a group represented by —S(O)_(n)—(CR₅R₆)_(m)—(wherein n is 2, m is 1 and R5 and R6 are a hydrogen atom); R₁ and R₂ are a methyl group; R₃ and R₄ are a hydrogen atom; and Y is a phenyl group substituted with 1 to 5 same or different R₇; R₇ is a hydrogen atom, a C₁ to C₃ alkyl group which may be substituted with 1 to 3 same or different halogen atoms, a C₁ to C₃ alkoxy group which may be substituted with 1 to 3 same or different halogen atoms, or a halogen atom.
 14. An isoxazoline compound or a salt according to claim 1, wherein n is 2, m is 1 and R₅ and R₆ are a hydrogen atom; R₁ and R₂ are each independently a C₁ to C₃ alkyl group; and Y is a phenyl group substituted with 1 to 5 same or different R₇; R₇ is a hydrogen atom, a halogen atom, a C₁ to C₃ alkyl group, a C₁ to C₃ alkoxy group, a C₁ to C₃ haloalkyl group or a C₁ to C₃ haloalkoxy group.
 15. An isoxazoline compound or a salt according to claim 14, wherein R₁ and R₂ are a methyl group; and R₇ is a is a hydrogen atom, F, Cl, Br, a C₁ to C₃ alkyl group, a C₁ to C₃ alkoxy group, a C₁ to C₃ fluoroalkyl group, a C₁ to C₃ chloroalkyl group, a C₁ to C₃ fluoroalkoxy group or a C₁ to C₃ chloroalkoxy group.
 16. A herbicidal formulation containing, as the active ingredient, an isoxazoline derivative or its salt set forth in claim
 7. 17. A herbicidal formulation containing, as the active ingredient, an isoxazoline derivative or its salt set forth in claim
 8. 18. A herbicidal formulation containing, as the active ingredient, an isoxazoline derivative or its salt set forth in claim
 9. 19. A herbicidal formulation containing, as the active ingredient, an isoxazoline derivative or its salt set forth in claim
 10. 20. A herbicidal formulation containing, as the active ingredient, an isoxazoline derivative or its salt set forth in claim
 11. 21. A herbicidal formulation containing, as the active ingredient, an isoxazoline derivative or its salt set forth in claim
 12. 22. A herbicidal formulation containing, as the active ingredient, an isoxazoline derivative or its salt set forth in claim
 13. 23. A herbicidal formulation containing, as the active ingredient, an isoxazoline derivative or its salt set forth in claim
 14. 24. A herbicidal formulation containing, as the active ingredient, an isoxazoline derivative or its salt set forth in claim
 15. 25. An isoxazoline compound or salt according to claim 1, wherein Q is a group represented by —S(O)_(n)—(CR₅R₆)_(m)- (wherein n is 2, m is 1 and R₅ and R₆ are a hydrogen atom); R₁ and R₂ are methyl group; R₃ and R₄ are a hydrogen atom; and Y is a phenyl group substituted with 1 to 5 same or different R₇; R₇ is a hydrogen atom, a chlorine atom or a C₁ to C₃ alkoxy group.
 26. An isoxazoline compound or salt according to claim 1, wherein Q is a group represented by —S(O)_(n)—(CR₅R₆)_(m)- (wherein n is 2, m is 1 and R₅ and R₆ are a hydrogen atom); R₁ and R₂ are methyl group; R₁ and R₄ are a hydrogen atom; and Y is a phenyl group substituted with 1 to 5 same or different R₇; R₇ is a hydrogen atom, a chlorine atom or a C₁ to C₃ fluoroalkoxy group.
 27. An isoxazoline compound or salt according to claim 1, wherein Q is a group represented by —S(O)_(n)—(CR₅R₆)_(m)- (wherein n is 2, m is 1 and R₅ and R₆ are a hydrogen atom); R₁ and R₂ are methyl group; R₃ and R₄ are a hydrogen atom; and Y is a phenyl group substituted with 1 to 5 same or different R₇; R₇ is a hydrogen atom, a chlorine atom or a 2-propynyloxy group. 